JP2015193596A - THIENOPYRAZINE DERIVATIVE HAVING p-SULFANYL-SUBSTITUTED PHENYL GROUPS AND METHOD FOR PRODUCING THE SAME - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel thienopyrazine derivative useful as a monomer which serves as a raw material of a low-bandgap (Eg<1.5 eV) conjugated polymer, and a method for producing the same.SOLUTION: Provided are a thienopyrazine derivative represented by the formula, and a method for producing the same. [Rand Rare each independently a substituted or unsubstituted aryl group.]

Description

  The present invention relates to a novel thienopyrazine derivative having a p-sulfanyl-substituted phenyl group, a method for producing the same, a halogenated thienopyrazine derivative useful as an intermediate for Suzuki polymerization, and a diphenylethanedione derivative that can be an intermediate of the novel thienopyrazine derivative. It relates to the manufacturing method.

  The condensed ring system [3,4-b] pyrazine derivative is an important compound for which synthesis of various derivatives has been attempted in order to modify solubility and active site in the field of medicine and agrochemicals. In recent years, in the field of functional materials, it is considered that thienopyrazine derivatives and quinoxaline derivatives condensed with a pyrazine ring can be used as monomers of low band gap (Eg <1.5 eV) conjugated polymers. Furthermore, the above-mentioned pyrazine derivatives and polymers obtained therefrom have been energetically studied for the synthesis of novel derivatives as organic semiconductor materials for the purpose of photoelectric conversion. Thin film solar cells (OPV), thin film transistors ( It is expected to be put to practical use in applications such as TFT).

  The fused ring pyrazine derivative is synthesized by the reaction of an aromatic diamine and an α-diketone. The polymer obtained from the pyrazine derivative is a promising material for use in material development in which the energy level of the lowest unoccupied orbit (LUMO) needs to be adjusted, and a lower band gap (Eg <1.5 eV) is required. It has been. For this reason, attempts have been made to introduce substituents into the pyrazine skeleton. In particular, the influence of the substituent of the α-diketone-derived moiety is important, and it was necessary to develop an α-diketone derivative having various substituents introduced as a raw material for the pyrazine derivative.

  α-Diketone derivatives are intermediates of thienopyrazine derivatives, and production methods such as Wurtz coupling reactions of acid halides, cryogenic reactions of carboxylic acid esters with alkyl metals and CO, and oxidation reactions of alkyne derivatives have been reported. . The production method using the reaction has drawbacks such as limitation of phenyl group and methyl group, handling of the reactants, synthesis of alkynes, and low yield. Therefore, a method for introducing a further substituent into the α-diketone derivative has been desired.

  JP 2012-56991 A (Patent Document 1) discloses a conductive thienopyrazine copolymer composition having a repeating unit represented by the following general formula (I):

The chemical formula in Patent Document 1 indicates a repeating unit of a polymer, and there is no description regarding a single thienopyrazine compound. R ¹ and R ² may be an aryl group or an alkyl group having 1 to 20 carbon atoms, and a methyl group and a phenyl group are exemplified, but there is no description about substituents of the aryl group.

上記の化合物ＤおよびＥを準備して、前記化合物Ｄと化合物Ｅとをモル比１：０．１〜１：１０の範囲で０〜７８℃の温度でメタノール、エタノール及び酢酸エチルから選択された少なくとも一つの溶媒に混合溶解し、該化合物Ｄに対してモル比で２〜５０倍のトリエチルアミン及び炭酸ナトリウムから選択された弱塩基を加えて１〜２４時間反応させることで

上記の化学式に示す化合物Ｆを得ることが記載されている。また、これから下記の化合物Ｃ：

を得ることが示されている。 In claim 5 of JP 2013-537564 A (Patent Document 2),

The above compounds D and E were prepared, and the compound D and the compound E were selected from methanol, ethanol and ethyl acetate at a temperature of 0 to 78 ° C. in a molar ratio range of 1: 0.1 to 1:10. By mixing and dissolving in at least one solvent, adding a weak base selected from triethylamine and sodium carbonate in a molar ratio of 2 to 50 times with respect to Compound D, and reacting for 1 to 24 hours.

It is described that the compound F shown in the above chemical formula is obtained. In addition, from now on, the following compound C:

Has been shown to get.

However, R ₃ and R ₄ of the compound described in Patent Document 2 are an alkyl group, an alkoxy group, or an aryl group, and do not represent a p-sulfanyl-substituted phenyl group.

JP 2012-56991 A Special table 2013-537564 gazette

  The present invention relates to a novel thienopyrazine derivative useful as a raw material for a low band gap (Eg <1.5 eV) conjugated polymer, a halogenated thienopyrazine derivative useful as an intermediate for Suzuki polymerization, and a method for producing the same. Is intended to provide.

  As a result of intensive studies, the present inventors have found a novel thienopyrazine derivative that is a raw material monomer for a conjugated polymer that is useful for an organic semiconductor material, and has found an inexpensive and high-yield production method.

  That is, the present invention provides a thienopyrazine derivative represented by the following general formula (1):

[式（１）中、Ｒ^１及びＲ^２は同一でも、異なっていてもよく、直鎖または分岐鎖のアルキル基または置換基を有していてもよいアリール基である。]

[In Formula (1), R ¹ and R ² may be the same or different, and are a linear or branched alkyl group or an aryl group optionally having a substituent. ]

In the general formula (1), the aryl groups of R ¹ and R ² are preferably a phenyl group which may have a substituent.

In the general formula (1), the alkyl groups of R ¹ and R ² are preferably branched alkyl groups having 4 to 8 carbon atoms.

[式（２）中、Ｒ^１及びＲ^２は同一でも、異なっていてもよく、直鎖または分岐鎖のアルキル基または置換基を有していてもよいアリール基である。]
で表されるジフェニルエタンジオン誘導体を、一般式（４）：

で表される３，４−ジアミノチオフェンとの反応により得られる上記チエノピラジン誘導体の製造方法を提供する。 The present invention also provides a general formula (2):

[In Formula (2), R ¹ and R ² may be the same or different, and are a linear or branched alkyl group or an aryl group optionally having a substituent. ]
A diphenylethanedione derivative represented by general formula (4):

The manufacturing method of the said thienopyrazine derivative obtained by reaction with 3,4-diaminothiophene represented by these is provided.

[式（８）中、Ｒ^１及びＲ^２は同一でも、異なっていてもよく、直鎖または分岐鎖のアルキル基または置換基を有していてもよいアリール基であり、Ｘ^２は、フッ素、塩素、臭素およびヨウ素から成る群から選択されるハロゲン原子、ボロン酸残基またはジオールまたはアルコールとホウ酸との反応により得られるボロン酸エステル残基である。]
で表されるハロゲン化チエノピラジン誘導体も提供する。 The present invention relates to a general formula (8)

[In Formula (8), R ¹ and R ² may be the same or different, and are a linear or branched alkyl group or an aryl group which may have a substituent, and X ² represents fluorine. A boron atom selected from the group consisting of chlorine, bromine and iodine, a boronic acid residue or a boronic acid ester residue obtained by reacting a diol or alcohol with boric acid. ]
A halogenated thienopyrazine derivative represented by the formula:

In the above formula (8), X ² is preferably iodine.

In the above formula (8), X ² is also preferably a boronic acid residue or a residue of a boronic acid ester obtained by reacting a diol or alcohol with boric acid.

In the general formula (8), the alkyl groups of R ¹ and R ² are preferably branched alkyl groups having 4 to 8 carbon atoms.

In the general formula (8), the aryl groups of R ¹ and R ² are preferably phenyl groups that may have a substituent.

[式（３）中、Ｘ^１は臭素または塩素である。]
で表されるジハロゲンベンジル化合物とチオール誘導体であるＲ^１−ＳＨおよびＲ^２−ＳＨ（Ｒ^１及びＲ^２は、同一でも、異なっていても良く、直鎖または分岐鎖のアルキル基または置換基を有していてもよいアリール基である。）を反応して得られる
一般式（２）：

[式（２）中、Ｒ^１及びＲ^２は同一でも、異なっていてもよく、直鎖または分岐鎖のアルキル基または置換基を有していてもよいアリール基である。]
で表されるジフェニルエタンジオン誘導体の製造方法も提供する。 Furthermore, the present invention further provides a general formula (3):

[In the formula (3), X ¹ is bromine or chlorine. ]
R ¹ —SH and R ² —SH (R ¹ and R ² may be the same or different, and may be a linear or branched alkyl group or substituent. Which is an aryl group which may have a general formula (2) obtained by reacting:

[In Formula (2), R ¹ and R ² may be the same or different, and are a linear or branched alkyl group or an aryl group optionally having a substituent. ]
The manufacturing method of the diphenylethanedione derivative represented by these is also provided.

  According to the present invention, a novel thienopyrazine derivative having a sulfanyl group represented by the general formula (1) can be provided. The novel thienopyrazine derivative is useful as a conductive material, and a polymer containing this as a constituent unit has good conductivity and is optimal as a polymer used for the conductive material.

  The present invention also provides a diphenylethanedione derivative that is an intermediate of the above thienopyrazine derivative. The diphenylethanedione derivative is an intermediate of a novel thienopyrazine derivative, and various substituents can be introduced into the phenyl group via a sulfur atom.

It is an ultraviolet visible spectrum of Example 6 and Comparative Example 2. It is an ultraviolet-visible spectrum of Examples 5-8 and Comparative Example 2.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

Hereinafter, the thienopyrazine derivative of the present invention will be described in detail.

(About the thienopyrazine derivative of the present invention)
The thienopyrazine derivative of the present invention has the following formula (1):

[式（１）中、Ｒ^１及びＲ^２は同一でも、異なっていてもよく、直鎖または分岐鎖のアルキル基または置換基を有していてもよいアリール基である。]
で表される。

[In Formula (1), R ¹ and R ² may be the same or different, and are a linear or branched alkyl group or an aryl group optionally having a substituent. ]
It is represented by

The linear or branched alkyl group for R ¹ and R ² in the above formula (1) is a linear or branched alkyl group having 1 to 18 carbon atoms, or an alicyclic alkyl having 3 to 18 carbon atoms. Groups. Specific examples of the linear or branched alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl. Group, t-butyl group, n-pentyl group, neo-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, lauryl group, Examples include stearyl groups.
Examples of the alicyclic alkyl group having 3 to 18 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
R ¹ and R ² are preferably a linear or branched alkyl group having 1 to 10 carbon atoms. Furthermore, R ¹ and R ² are preferably a branched alkyl group having 3 to 10 carbon atoms. More preferably, R ¹ and R ² are branched alkyl groups having 4 to 8 carbon atoms. More specifically, examples of R ¹ and R ² include i-butyl group, sec-butyl group, t-butyl group, i-pentyl group, and 2-ethylhexyl group.

The aryl group which may have a substituent in R ¹ and R ² is, for example, an aryl group having 6 to 18 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group.

  Examples of the substituent in the aryl group include linear or branched alkyl groups, alkoxy groups, haloalkyl groups, aryl groups, heteroaryl groups, and hydroxyl groups.

  The linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, and more specifically, a methyl group, an ethyl group, an n-propyl group, i- Propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, neo-pentyl group, n-hexyl group, n-heptyl group, n- Examples include octyl group, 2-ethylhexyl group, n-decyl group, lauryl group, stearyl group and the like. In particular, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. Further, i-butyl group, sec-butyl group, t-butyl group, i-pentyl group, and 2-ethylhexyl group are preferable.

  Examples of the alkoxy group include an alkoxy group having 1 to 18 carbon atoms, and more specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and an i-butoxy group. , Sec-butoxy group, t-butoxy group, n-pentyloxy group, neo-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group and the like.

The haloalkyl group refers to an alkyl group to which a halogen atom (F, Cl, Br, I) is added. In this case, examples of the alkyl group include the alkyl groups having 1 to 18 carbon atoms. As the halogen atom, fluorine is preferred. More specifically, a perfluoroalkyl group C _p F _{2p + 1} − exemplified by CF ₃ group, C ₂ F ₅ group, n-C ₃ F ₇ group, n-C ₄ F ₉ , n-C ₇ F ₁₅ group and the like. Groups (p = 1-18); partial fluoroalkyl groups exemplified by CHF ₂ groups, CH ₂ F groups, CH (CF ₃ ) ₂ groups, and the like.

  As said aryl group, a C6-C18 aryl group is mentioned, for example, Specifically, a phenyl group, a naphthyl group, etc. are mentioned.

  Examples of the heteroaryl group include heteroaryl groups having 4 to 10 carbon atoms, and specific examples include a thienyl group, a pyrrolyl group, a furyl group, and a pyridyl group.

  Specific examples of the thienopyrazine derivative (1) of the present invention are shown in Tables 1 and 2 below. The thienopyrazine derivative of the present invention is not limited to these.

Table 1 shows specific examples of the thienopyrazine derivative (1) when R ¹ and R ² are linear or branched alkyl groups. Note that the derivatives of the present invention are not limited to these.

  In the present specification, i-Pro is an isopropyl group, i-Pen is an isopentyl group, n-Oct is an octyl group, n-Dcy is a decyl group, 2-EtHx is 2-ethylhexyl, which are described as substituents in the following table. The group CyHx represents a cyclohexyl group.

Table 2 shows specific examples of the thienopyrazine derivative (1) when R ¹ and R ² are aryl groups. For convenience, the following thienopyrazine derivative (1 ′) was used to indicate the position of the substituent. Table 2 specifically shows the substituents of the phenyl-S-group and the substitution positions thereof.
Note that the derivatives of the present invention are not limited to these.

(Method for producing thienopyrazine derivative)
Although the synthesis method of the thienopyrazine derivative of this invention is illustrated and demonstrated, this invention is not limited to these specific examples.

  The method for producing a thienopyrazine derivative of the present invention is a production method including at least a step I: a step of obtaining a thienopyrazine derivative by reacting a diphenylethanedione derivative having a sulfanyl group with diaminothiophene.

  Further, the production method may include, as a pre-step of Step I, Step II: a step of reacting dihalogenphenylethanedione and thiol to obtain a diphenylethanedione derivative having a sulfanyl group.

  As shown in the following reaction formula (3), the thienopyrazine derivative (1) of the present invention includes a diphenylethanedione derivative (2) having various substituents via a sulfur atom and 3,4-diaminothiophene ( Obtained by the reaction of 4).

[式（３）中、Ｒ^１及びＲ^２は前記と同意義である。]

[In formula (3), R ¹ and R ² are as defined above. ]

  The thienopyrazine derivative (1) of the present invention has a molar ratio of 1: 1 between the diphenylethanedione derivative (2) and 3,4-diaminothiophene (4) as shown in the chemical reaction formula (3), for example. It mixes so that it may melt | dissolve in a reaction solvent, an acid or a base is added, and it can obtain by reacting at the temperature of 0-78 degreeC for 1 to 24 hours.

  Examples of the reaction solvent include lower alcohols having 1 to 3 carbon atoms such as methanol and ethanol.

  Examples of the acid include inorganic acids such as hydrochloric acid and organic acids such as acetic acid. Organic acids, particularly acetic acid, are preferred. The acid is added to promote the dehydration reaction, and the addition amount is preferably 2 equivalents or more.

  Examples of the base include inorganic bases such as sodium carbonate and potassium carbonate, and organic bases such as triethylamine. The base is added to promote dehydration, and the addition amount is preferably 2 equivalents or more.

  The reaction temperature, reaction time, and the like can be appropriately selected under conditions suitable for the reaction system. For example, the reaction can be carried out at 0 to 78 ° C. for 1 to 24 hours. A reaction vessel suitable for the reaction conditions can be used as appropriate.

[式（２）中、Ｒ^１及びＲ^２は同一でも、異なっていてもよく、直鎖または分岐鎖のアルキル基または置換基を有していてもよいアリール基である。]で表される。 (Diphenylethanedione derivative (2))
The diphenylethanedione derivative (2) used for the synthesis of the thienopyrazine derivative (1) is represented by the following formula (2):

[In Formula (2), R ¹ and R ² may be the same or different, and are a linear or branched alkyl group or an aryl group optionally having a substituent. It is represented by

  Specific examples of the diphenylethanedione derivative of the present invention are shown in Table 3 below. Note that the derivatives of the present invention are not limited to these. In Table 3, * indicates a binding site with sulfur.

The diphenylethanedione derivative (2) can be synthesized by various known methods. For example, according to the following reaction formula (5), the dihalogenphenylethanedione derivative (6) is used as a starting material, and in the presence of a base, It can be easily synthesized by reacting with a thiol (R-SH) having a group or an aryl group. In the reaction formula (5), the diphenylethanedione derivative represented by the formula (7) shows the case where R ¹ and R ² are R in the diphenylethanedione derivative (2).

［上記反応式中、Ｒは直鎖または分岐鎖のアルキル基または置換基を有していてもよいアリール基であり、Ｘ^１は、塩素または臭素である。］

[In the above reaction formula, R is a linear or branched alkyl group or an aryl group which may have a substituent, and X ¹ is chlorine or bromine. ]

  The diphenylethanedione derivative (7) can be obtained, for example, by reacting the dihalogenphenylethanedione derivative (6) with a thiol (R-SH) in the presence of a base in a solvent.

  Examples of the dihalogenphenylethanedione derivative (6) include 4,4'-dichlorobenzyl and 4,4'-dibromobenzyl. Examples of commercially available products include 4,4'-dibromobenzyl (manufactured by Tokyo Chemical Industry Co., Ltd.).

Specific examples of the thiol (R-SH) include linear or branched alkyl thiols such as 1-propanethiol, 2-propanethiol, 1-butanethiol, 2-butanethiol, t-butanethiol, 1- Such as pentanethiol, 2-pentanethiol, 1-decanethiol;
Arylthiols such as benzenethiol, p-hydroxybenzenethiol, p-toluenethiol, 4-ethylbenzenethiol, 2-methoxybenzenethiol, p-trifluoromethylbenzenethiol, 1-naphthalenethiol, 2-naphthalenethiol; It is done. Examples of commercially available products include 1-pentanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.) and benzenethiol (manufactured by Tokyo Chemical Industry Co., Ltd.). In the above reaction formula (5), the case of R ¹ = R ² = R is shown. However, when R ¹ and R ² are different, two different thiols are added sequentially or two different thiols are added. It is obtained by mixing and using.

  The solvent is not particularly limited as long as the reaction raw material dissolves. A polar aprotic solvent can be preferably used. Examples of polar aprotic solvents that can be used include tetrahydrofuran (THF), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and the like. DMF is particularly preferable.

  The base is not particularly specified as long as it is a general base, and any base can be used, but an alkali metal such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or the like can be used. Examples thereof include alkaline earth metal hydroxides and tertiary amines such as trimethylamine, triethylamine, tributylamine, triethanolamine, and pyridine.

  The base is not particularly limited as long as the reaction proceeds, but is preferably 2 equivalents or more with respect to the dihalogenphenylethanedione derivative.

  Since the thienopyrazine derivative of the present invention has various substituents on diphenylethane through a sulfur atom (S), it is presumed that the band gap can be narrowed. This is because the sulfur atom (S) has a high electron donating property, and therefore the non-localization of the highest occupied orbital (HOMO) of the whole molecule of the pyrazine ring, and hence the thienopyrazine derivative, via the phenyl group having π electrons. As a result, the difference in the lowest orbit (LUMO), that is, the so-called band gap is expected to be narrowed. Therefore, the thienopyrazine derivative of the present invention is useful as a monomer of a low band gap (Eg <1.5 eV) conjugated polymer, and can be used as a p-type organic semiconductor. In addition, according to the production method of the present invention, it is possible to design and develop condensed rings containing a wide variety of pyrazine rings including thieno [3,4-b] pyrazine.

(Halogenated thienopyrazine derivative (8))
The halogenated thienopyrazine derivative (8) of the present invention can be obtained by subjecting the thienopyrazine derivative (1) to a halogenation reaction or a boron oxidation reaction (boronic acid or boronic acid esterification). The obtained halogenated thienopyrazine derivative can be an effective material as a raw material monomer for the polymerization reaction. A low band gap conjugated polymer suitable for an organic thin film solar cell can be obtained by using the halogenated thienopyrazine derivative as a monomer and using a known polymerization reaction, preferably by Suzuki polymerization. In the present specification, the thienopyrazine derivative subjected to the halogenation reaction and the thienopyrazine derivative subjected to the boron oxidation reaction are collectively referred to as a halogenated thienopyrazine derivative.

[式（８）中、Ｒ^１及びＲ^２は、同一でも、異なっていてもよく、直鎖または分岐鎖のアルキル基または置換基を有していてもよいアリール基であり、Ｘ^２は、例えばフッ素、塩素、臭素およびヨウ素から成る群から選択されるハロゲン原子、ボロン酸残基またはジオールまたはアルコールとホウ酸との反応により得られるボロン酸エステル残基である。]を有する。 The halogenated thienopyrazine derivative (8) has the following chemical formula:

[In Formula (8), R ¹ and R ² may be the same or different, and are a linear or branched alkyl group or an aryl group optionally having a substituent, and X ² is For example, a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine, a boronic acid residue or a boronic acid ester residue obtained by reacting a diol or alcohol with boric acid. ]

In the above formula (8), the alkyl groups of R ¹ and R ² are the same as those described for the thienopyrazine derivative (1), and are preferably branched alkyl groups having 4 to 8 carbon atoms.

In the above formula (8), the case where X ² is a halogen atom will be described. The halogen atom is selected from the group consisting of fluorine, chlorine, bromine and iodine, and iodine is particularly preferable.

  The halogenation reaction for synthesizing the halogenated thienopyrazine derivative is halogenated using a general halogenating agent. Examples of halogenating agents include N-fluorobenzenesulfonimide, N-bromosuccinimide, dibromoisocyanuric acid, N-iodosuccinimide, 1,3-diiodo-5,5′-dimethylhydantoin, potassium iodide / periodic acid Although potassium, copper iodide, etc. are mentioned, it is not limited to these.

The case where X ² is a boronic acid residue or a boronic acid ester residue will be described. X ² is a boronic acid residue (—B (OH) ₂ ) or a boronic acid ester residue (—B (OR ^P ) ₂ ) obtained by reacting a diol or alcohol with boric acid; R ^P is a diol or alcohol And a boronic acid ester residue obtained by reacting a diol or alcohol with boric acid. More specifically, the boronic acid ester includes boric acid, diols having 1 to 7 carbon atoms such as pinacol, catechol, neopentyl glycol, 1,2-ethanediol, 1,3-propanediol, methanol, ethanol, isopropanol. , A boric acid ester residue obtained by reaction with an alcohol having a linear or branched alkyl group having 1 to 10 carbon atoms such as t-butanol.

Examples of the boronic acid ester residue include groups represented by the following formulas (a) to (e). The boronic acid ester residue is not limited to these.

  When the boric acid ester residue is reacted with the general formula (1) to form a boronic acid ester, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane or 2- A reagent such as isopropoxy-4,4,6-trimethyl-1,3,2-dioxaborinane (manufactured by Tokyo Chemical Industry Co., Ltd.) can be used.

  Specific examples of the halogenated thienopyrazine derivative of the present invention are shown in Table 4 below. Note that the derivatives of the present invention are not limited to these. In Table 4, * indicates a binding site with sulfur. The boronic esters of the formulas (a) to (e) represent the boronic esters described above.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, it should not be understood that the scope of the present invention is limited to these examples.

(Example 1)
[Compound 1-a] Synthesis of 1,2-di (4-n-octylsulfanylphenyl) ethanedione In a 50 ml three-necked flask, 14 ml of N, N-dimethylformamide (DMF) and 0.38 g (2.7 mmol, potassium carbonate) 0 eq.), 0.5 g (1.36 mmol) of dibromobenzyl and 0.42 g (2.86 mmol) of 1-octanethiol were added, and the mixture was heated and stirred at 60 ° C. for 9 hours. After 3 hours and 6 hours, 0.38 g of potassium carbonate was sequentially added. After 9 hours, the mixture was allowed to cool to room temperature, and then the reaction solution, 50 ml of tap water, and 50 ml of ethyl acetate were put into a 300 ml separatory funnel. The organic layer was separated, the aqueous layer was extracted twice with 50 ml of ethyl acetate, and the organic layer was washed successively with 100 ml of saturated aqueous sodium hydrogen carbonate solution, 100 ml of tap water, and 100 ml of saturated aqueous sodium chloride solution. After adding magnesium sulfate and dehydrating the organic layer, the added magnesium sulfate was filtered, and the organic solvent was distilled off under reduced pressure using an evaporator. 0.75 g of a yellow solid was obtained. The yellow fraction of Rf = 0.7 was fractionated by column chromatography (silica gel 70 g, toluene: hexane = 1: 1 1.4 L). Concentration by an evaporator gave 0.26 g (yield 38.2%) of yellow solid 1,2-di (4-n-octylsulfanylphenyl) ethanedione.

About the obtained [compound 1-a], an elemental analyzer (EA: Perkin Elmer Japan Co., Ltd. 2400II fully automatic elemental analyzer), ¹ H-nuclear magnetic resonance apparatus, ¹³ C-nuclear magnetic resonance apparatus (NMR: JNM-AL300 manufactured by JEOL Ltd., Fourier transform infrared spectrophotometer (FT-IR: JIR-SPX60S manufactured by JEOL Ltd.), gas chromatography mass spectrometer (GC / MS: GC / MS Spectrometer manufactured by Agilent Technologies) 6890N / 5973N) and differential thermal / thermogravimetric measurement (TG / DTA: TG / DTA6200 manufactured by SII Nano Technologies) are shown below. From these results, it was confirmed that [Compound 1-a] has the structure of the formula (9).

Compound _{1-a C 30 H 42 O} 2 S 2 Molecular weight 498.8

¹ H-NMR (CDCl ₃ , 300 MHz):
0.88 (6H, t, _JH-H = 6.9 Hz), 1.43 (16H, m), 1.65 (4H, m), 1.73 (4H, m), 2.99 (4H) , T, J _H-H = 7.2 Hz), 7.29 (4H, dd, J _H-H = 4.8 Hz, J _H-H = 1.8 Hz), 7.83 (4H, dd, J _{H -H} = 4.8Hz, _JH-H = 1.8Hz)
¹³ C-NMR (CDCl ₃ , 75.45 Hz):
14.1, 22.6, 28.6, 28.9, 29.1, 31.7, 31.8, 126.0, 129.4, 130.2, 148.1, 193.5
IR (KBr pellet):
2954 (m), 2922 (s) 2850 (m), 1659, 1667 (s), 1535, 1489, 1466, 1400, 1335, 1226, 1176, 1097, 1083 (m), 883, 817 (s), 759 , 744, 696, 542, 488 (m)
GC-MS: m / z = 249.10 (100%), 498.30 (0.56%)
m. p. : 60.8 ° C

(Example 2)
[Compound 3-a] Synthesis of 1,2- (4-i-pentylsulfanylphenyl) ethanedione In a 200 ml four-necked flask, 140 ml of DMF, 3.8 g (27 mmol, 2.0 eq.) Of potassium carbonate, 5.0 g of dibromobenzyl ( 14 mmol) and 3.0 g (29 mmol) of i-pentanethiol were added, and the mixture was heated and stirred at 60 ° C. for 9 hours. After 3 hours and 6 hours, 3.8 g of potassium carbonate was sequentially added. After 9 hours, the mixture was allowed to cool to room temperature, and then the reaction solution, 200 ml of tap water and 200 ml of ethyl acetate were put into a 1 L separatory funnel. The organic layer was separated, the aqueous layer was extracted twice with 200 ml of ethyl acetate, and the organic layer was washed successively with 200 ml of saturated aqueous sodium hydrogen carbonate solution, 200 ml of tap water and 200 ml of saturated aqueous sodium chloride solution. After adding magnesium sulfate and dehydrating the organic layer, the added magnesium sulfate was filtered, and the organic solvent was distilled off under reduced pressure using an evaporator. 6.2 g of a yellow liquid was obtained. The yellow fraction of Rf = 0.6 was fractionated by column chromatography (silica gel 120 g, toluene: hexane = 1: 1 1.5 L). Concentration with an evaporator gave 3.3 g (yield 63.0%) of yellow liquid 1,2-di (4-i-pentylsulfanylphenyl) ethanedione.

The obtained [Compound 3-a] was subjected to elemental analysis and ¹ H-NMR, ¹³ C-NMR, IR, GC / MS, and TG / DTA measurement in the same manner as in Example 1. The results are shown below. From these results, it was confirmed that [Compound 3-a] had the structure of the formula (10).

Compound _{3-a C 24 H 30 O} 2 S 2 Molecular weight 414.6

¹ H-NMR (CDCl ₃ , 300 MHz):
0.95 (d, 12H, _JH-H = 6.3 Hz), 1.59 (m, 4H), 1.73 (m, 2H), 3.00 (t, 4H, _JH-H = 7 .8 Hz), 7.29 (m, 4H), 7.84 (4H, m)
¹³ C-NMR (CDCl ₃ , 75.45 Hz):
22.2, 27.6, 29.7, 126.0, 129.4, 130.2, 148.0, 193.5
IR (NaCl):
2956 (s), 2927, 2870 (m), 1668, 1585 (vs), 1554 (s), 1488, 1467, 1403 (m), 1279 (w), 1216, 1176, 1089 (s), 879, 831 , 765, 682 (ms), 542 (w)
GC-MS: m / z = 207.05 (100%), 414.20 (1.83%)
m. p. : 39.3 ° C

(Example 3)
[Compound 16-a] Synthesis of 1,2-di (4- (p-hydroxyphenyl) sulfanylphenyl) ethanedione In a 50 ml three-necked flask, 14 ml of DMF, 0.38 g of potassium carbonate (2.7 mmol, 2.0 eq.), Dibromo 0.5 g (1.36 mmol) of benzyl and 0.36 g (2.86 mmol) of p-hydroxybenzenethiol were added, followed by heating and stirring at 60 ° C. for 4 hours and at 80 ° C. for 4 hours. After 3 hours and 6 hours, 0.38 g of potassium carbonate was sequentially added. After 8 hours, the mixture was allowed to cool to room temperature, and the reaction solution, 50 ml of tap water and 50 ml of toluene were put into a 300 ml separatory funnel. The organic layer was separated, and the aqueous layer was extracted twice with 50 ml of toluene. The obtained organic layer was sequentially washed with 100 ml of saturated aqueous sodium hydrogen carbonate solution, 100 ml of tap water, and 100 ml of saturated aqueous sodium chloride solution. After adding magnesium sulfate and dehydrating the organic layer, the added magnesium sulfate was filtered, and the organic solvent was distilled off under reduced pressure using an evaporator. 0.56 g of a yellow solid was obtained. The yellow fraction of Rf = 0.3 was fractionated by column chromatography (silica gel 70 g, toluene: ethyl acetate = 1: 1: 0.6 L). When concentrated by an evaporator, 0.44 g of a yellow solid was obtained.

  The obtained solid was dissolved in 100 ml of ethyl acetate and washed sequentially with 100 ml of 1.0 M aqueous sodium hydroxide solution and 50 ml of saturated aqueous sodium chloride solution. The organic layer was dehydrated with magnesium sulfate, the added magnesium sulfate was filtered, and the organic solvent was distilled off under reduced pressure using an evaporator. Further, reprecipitation purification was performed with chloroform / hexane to obtain 0.18 g (yield 28.8%) of yellow solid 1,2-di (4- (p-hydroxyphenyl) sulfanylphenyl) ethanedione.

About the obtained [Compound 16-a], as in Example 1, ¹ H-NMR, ¹³ C-NMR, IR, liquid chromatography mass spectrometer (LC / MS: LC / 3DQMS M manufactured by Hitachi High-Technologies Corporation) -8000), and TG / DTA was measured. The results are shown below. From these results, it was confirmed that [Compound 16-a] had the structure of the formula (11).

Compound _{16-a C 26 H 18 O} 4 S 2 Molecular weight 458.6

¹ H-NMR (DMSO-d6, 300 MHz):
6.90 (4H, d, _JH-H = 8.4 Hz), 7.13 (4H, d, _JH-H = 8.4 Hz), 7.40 (4H, d, _JH-H = 8) .4 Hz), 7.73 (4H, d, J _H-H = 8.4 Hz), 10.1 (2H, s)
¹³ C-NMR (DMSO-d6, 75.45 MHz):
116.8, 117.2, 125.3, 128.7, 130.1, 137.1, 150.0, 159.2, 193.5
IR (KBr):
3548 (m), 3373 (br-m), 1660, 1647 (m), 1585 (vs), 1554, 1495 (m), 1440, 1404, 1365, 1328 (w), 1267, 1234, 1220, 1172, 1078 (m), 1010 (w), 881, 827 (m), 767, 756, 735, 698, 525, 480 (w)
LC-MS: m / z = 457.33 (ESI-)
m. p. : 157.0 ° C

(Example 4)
[Compound 17-a] Synthesis of 1,2-di (4- (p-trifluoromethylphenyl) sulfanylphenyl) ethanedione In a 50 ml three-necked flask, 14 ml of DMF and 0.38 g of potassium carbonate (2.7 mmol, 2.0 eq.) , 0.5 g (1.36 mmol) of dibromobenzyl and 0.55 g (2.86 mmol) of p-trifluoromethylbenzenethiol were added, and the mixture was heated and stirred at 60 ° C. for 4 hours and at 80 ° C. for 4 hours. After 3 hours and 6 hours, 0.38 g of potassium carbonate was sequentially added. After 8 hours, the mixture was allowed to cool to room temperature, and the reaction solution, 50 ml of tap water and 50 ml of toluene were put into a 300 ml separatory funnel. The organic layer was separated, and the aqueous layer was extracted twice with 50 ml of toluene. Further, the organic layer was washed successively with 100 ml of saturated aqueous sodium hydrogen carbonate solution, 100 ml of tap water, and 100 ml of saturated aqueous sodium chloride solution. After adding magnesium sulfate and dehydrating the organic layer, the added magnesium sulfate was filtered, and the organic solvent was distilled off under reduced pressure using an evaporator. 0.62 g of a yellow solid was obtained. The yellow fraction of Rf = 0.6 was fractionated by column chromatography (silica gel 70 g, toluene: hexane = 1: 1 0.5 L). When concentrated with an evaporator and purified by reprecipitation with 40 ml of hexane, 0.10 g of white solid 1,2-di (4- (p-trifluoromethylphenyl) sulfanylphenyl) ethanedione was obtained (yield 13.4%). )Obtained.

About the obtained [compound 17-a], as in Example 1, elemental analysis and ¹ H-NMR, ¹³ C-NMR, ¹⁹ F-NMR (NMR: JNM-AL300 manufactured by JEOL Ltd.), IR, GC / MS and TG / DTA were measured. The results are shown below. From these results, it was confirmed that [Compound 17-a] had the structure of the formula (12).

Compound _{17-a C 28 H 16 F} 6 O 2 S 2 Molecular weight 562.6

¹ H-NMR (CDCl ₃ , 300 MHz):
7.32 (4H, dd, _JH-H = 8.4, _JH-H = 1.8), 7.55 (4H, d, _JH-H = 8.4), 7.63 (4H , D, J _H-H = 8.4), 7.86 (4H, dd, J _H-H = 8.4, J _H-H = 1.8)
¹³ C-NMR (CDCl ₃ , 75.45 MHz):
_{123.8 (q, J C-F} = 271.8Hz), 126.5 (q, J C-F = 3.8Hz), 129.0, 130.60 (q, J C-F = 33.0 ), 130.61, 131.3, 132.8, 137.4, 145.3, 192.9
¹⁹ F-NMR (CDCl ₃ , 98.7 MHz), Ref = HFB):
98.7 ppm
IR (KBr):
3080, 3049 (w), 1678, 1668 (s), 1605 (w), 1587 (s), 1558, 1488, 1400 (m), 1327 (vs), 1220 (m), 1169, 1128 (s), 1105, 1065, 1014, 889 (m), 835 (s), 825, 760 (m), 704, 690, 596, 488, 476 (w)
GC-MS: m / z = 281.0 (100%), 562.10 (0.29%)
m. p. : 120.0 ° C

(Example 5)
[Compound 1] Synthesis of 2,3-di (4-n-octylsulfanylphenyl) thieno [3,4-b] pyrazine 25 ml 10 ml ethanol in an eggplant flask, 22.9 mg (0.20 mmol) 3,4-diaminothiophene Then, 0.1 g (0.2 mmol) of 1,2-di (4-noctylsulfanylphenyl) ethanedione synthesized in Example 1 and 0.07 ml (1.2 mmol, 6.0 eq.) Of acetic acid were added at room temperature. Stirring was performed for 23 hours. The mixture was cooled in an ice bath, filtered, washed with 5 ml of cold ethanol, and dried under reduced pressure at 30 ° C. for 20 hours, so that light green solid 2,3-di (4-n-octylsulfanylphenyl) thienopyrazine was reduced to 0. .10 g (yield 86.3%) was obtained.

The obtained [Compound 1] was subjected to elemental analysis and ¹ H-NMR, ¹³ C-NMR, IR, LC / MS, and TG / DTA in the same manner as in Example 1 or Example 3. The results are shown below. From these results, it was confirmed that [Compound 1] had the structure of the formula (13).

Compound 1 C ₃₄ H ₄₄ N ₂ S ₃ molecular weight 576.9

¹ H-NMR (CDCl ₃ , 300 MHz):
0.88 (6H, t, _JH-H = 6.6 Hz), 1.27 (18H, s), 1.42 (4H, m), 1.66 (4H, m), 2.93 (4H , T, J _H-H = 6.6 Hz), 7.24 (4H, m), 7.36 (4H, m)
¹³ C-NMR (CDCl ₃ , 75.45 MHz):
14.1, 22.6, 28.90, 28.94, 29.16, 29.18, 31.8, 32.8, 117.4, 127.5, 130.0, 136.1, 139. 0, 141.6, 152.6
IR (KBr):
3093 (w), 2951 (m), 2922 (vs), 2850, 1591 (m), 1491 (w), 1468 (m), 1439, 1396, 1360, 1311, 1288, 1267, 1190 (w), 1097 (S), 1049 (w), 1011, 972, 858, 842, 833, 821, 804, 754 (m), 740, 721, 615, 540, 503 (w)
LC-MS m / z = 577.40 (APCI +)
m. p. : 92.1 ℃

(Example 6)
[Compound 3] Synthesis of 2,3-di (4-i-pentylsulfanylphenyl) thieno [3,4-b] pyrazine 110 ml of ethanol in a 500 ml four-necked flask and 1,2-di (4 synthesized in Example 2 -I-Pentylsulfanylphenyl) ethanedione 1.0 g (2.8 mmol) was added and cooled in an ice bath. 3,5-Diaminothiophene 0.35 g (2.8 mmol) and acetic acid 0.9 ml (16.5 mmol, 6.0 eq.) Were added, and the mixture was stirred in an ice bath for 30 minutes and at room temperature for 3 hours. . 200 ml of ethyl acetate and 200 ml of tap water were added. The organic layer was separated, the aqueous layer was extracted twice with 100 ml of ethyl acetate, the organic layers were combined, and washed successively with 100 ml of tap water and 100 ml of saturated aqueous ammonium chloride solution. Dehydration with magnesium sulfate, filtration, and evaporation were performed to obtain 1.2 g of a yellow solid. The yellow fraction of Rf = 0.4 was separated by column chromatography (silica gel 100 g, toluene: ethyl acetate = 20: 1 1.0 L) to obtain 1.2 g of a yellow solid. Further purification by reprecipitation with 3 ml of chloroform / 30 ml of hexane and drying under reduced pressure at 40 ° C. for 16 hours gave yellow solid 2,3-di (4-i-pentylsulfanylphenyl) thieno [3,4-b. There was obtained 1.0 g (yield 74.8%) of pyrazine.

The obtained [Compound 3] was subjected to elemental analysis and ¹ H-NMR, ¹³ C-NMR, IR, LC / MS, and TG / DTA in the same manner as in Example 1 or Example 3. The results are shown below. From these results, it was confirmed that [Compound 3] had the structure of the formula (14).

Compound 3 C ₂₈ H ₃₂ N ₂ S ₃ molecular weight 492.8

¹ H-NMR (CDCl ₃ , 300 MHz):
0.92 (12H, d, _JH-H = 6.6 Hz), 1.54 (4H, m), 1.73 (2H, m), 2.93 (4H, t, 7.8 Hz), 7 .23 (4H, dd, _JH-H = 6.9 Hz, _JH-H = 1.8 Hz), 7.36 (4H, dd, _JH-H = 8.7 Hz, _JH-H = 1. 8Hz), 8.01 (2H, s)
¹³ C-NMR (CDCl ₃ , 75.45 MHz):
22.3, 27.5, 30.9, 37.8, 117.4, 127.5, 130.0, 136.1, 138.9, 141.6, 152.6
IR (KBr):
3103 (w), 2953 (s), 2931, 2924, 2868 (m), 1593 (s), 1489, 1466, 1421, 1365, 1358, 1311 (w), 1281 (m), 1227, 1188 (w) , 1093 (vs), 1049, 1012, 970, 864, 837, 825 (m), 764 (s), 729, 669, 613, 593, 548 (w)
LC-MS: m / z = 493.53 (APCI +)
m. p. : 141.5 ° C

(Example 7)
[Compound 16] Synthesis of 2,3-di (4- (p-hydroxyphenyl) sulfanylphenylthieno [3,4-b] pyrazine 25 ml 10 ml of ethanol and 24.9 mg of 3,4-diaminothiophene (0. 22 mmol), 1,2-di (4- (p-hydroxyphenyl) sulfanylphenyl) ethanedione synthesized in Example 3, 0.1 g (0.22 mmol), acetic acid 0.08 ml (1.3 mmol, 6.0 eq.) The mixture was stirred for 8 hours at 60 ° C. Ethyl acetate (20 ml) and saturated aqueous ammonium chloride solution (20 ml) were added, the organic layer was separated, and the organic layer was washed twice with saturated aqueous ammonium chloride solution (20 ml) and saturated brine (20 ml). After dehydration with magnesium sulfate, filtration, and concentration with an evaporator, 0.11 g of a brown solid was obtained. The fraction of Rf = 0.8 was separated by column chromatography (silica gel 80 g, hexane: ethyl acetate = 1: 1 0.5 L), concentrated with an evaporator, and dried under reduced pressure at 50 ° C. for 16 hours, 43.8 mg (yield 37.1%) of orange solid 2,3-di (4- (p-hydroxyphenyl) sulfanylphenyl) thieno [3,4-b] pyrazine was obtained.

The obtained [Compound 16] was subjected to elemental analysis and ¹ H-NMR, ¹³ C-NMR, IR, LC / MS, and TG / DTA measurement in the same manner as in Example 1 or Example 3. The results are shown below. From these results, it was confirmed that [Compound 16] had the structure of the formula (15).

Compound _{16 C 30 H 20 N 2 O} 2 S 3 molecular weight 536.7

¹ H-NMR (DMSO-d6, 300 MHz):
6.87 (4H, d, _JH-H = 8.7 Hz), 6.90 (4H, d, _JH-H = 8.1 Hz), 7.29 (4H, d, 8.4 Hz), 7 .35 (4H, d, J _H-H = 8.4 Hz), 8.34 (2H, s), 9.97 (2H, br-s)
¹³ C-NMR (DMSO-d6, 75.45 MHz):
116.8, 118.3, 119.2, 125.7, 130.1, 135.9, 136.2, 140.1, 140.7, 151.8, 158.5
IR (KBr):
3105 (br-m), 1591 (vs), 1579 (s), 1493 (vs), 1427, 1369, 1309 (m), 1269 (vs), 1248 (m), 1217 (vs), 1167, 1086 ( m), 1051, 1010, 976, 864 (w), 825 (m), 766, 542, 528 (w)
LC-MS: m / z = 534.93 (ESI-)
m. p. : 261 ° C

(Example 8)
[Compound 17] Synthesis of 2,3-di (4- (p-trifluoromethylphenyl) sulfanylphenylthieno [3,4-b] pyrazine 1,2-di (4 synthesized in Example 4 in a 100 ml three-necked flask -(P-trifluoromethylphenyl) sulfanylphenyl) ethanedione (0.40 g, 0.71 mmol) and ethanol (40 ml) were added, and the mixture was stirred at room temperature for 10 minutes, and then 3,81-diaminothiophene (0.081 g, 0.71 mmol). Then, 0.24 ml (4.26 mmol, 6.0 eq.) Of acetic acid was added, and the mixture was stirred at room temperature for 2 hours, and then heated to 50 ° C. and stirred for 1 hour. The mixture was cooled to 5 ° C., the precipitate was collected by filtration, washed with 25 ml of ethanol at 10 ° C. or lower, dried under reduced pressure at 40 ° C. for 16 hours, and then green solid 2,3-di (4- (p-tri Le Oro methylphenyl) sulfanyl phenyl) thieno [3,4-b] pyrazine was obtained yield 0.38 g (83.5% yield).

For the obtained [Compound 17], elemental analysis and measurement of ¹ H-NMR, ¹³ C-NMR, ¹⁹ F-NMR, IR, LC / MS, TG / DTA) were carried out in the same manner as in Example 1 or Example 3. I did it. The results are shown below. From these results, it was confirmed that [Compound 17] had the structure of the formula (16).

Compound 17 C ₃₂ H ₁₈ F ₆ N ₂ S ₃ molecular weight 640.7

¹ H-NMR (CDCl ₃ , 300 MHz):
7.32 (4H, d, _JH-H = 8.1 Hz), 7.38 (4H, m), 7.45 (4H, m), 7.50 (4H, d, _JH-H = 8) .1Hz), 8.09 (2H, s)
¹³ C-NMR (CDCl 3, 75.45 MHz):
_{118.1, 124.0 (q, J C} -F = 272Hz), 126.0 (q, J C-F = 4.4Hz), 128.7 (q, J C-F = 32.4Hz), 129.4, 130.8, 132.2, 134.8, 138.8, 141.3, 141.5, 152.1
¹⁹ F-NMR (CDCl ₃ , 98.7 MHz), Ref = HFB):
98.8ppm
IR (KBr):
3059, 1606 (m), 1593, 1495 (w), 1402 (m), 1327 (vs), 1282 (w), 1169 (m), 1128 (s), 1086, 1065 (m), 1049 (w) , 1012, 972, 825 (m), 760, 752 (w), 600 (m), 546 (w)
LC-MS: m / z = 641.13 (APCI +)
m. p. : 173.0 ° C

Example 9
[Compound 20] Synthesis of 5,7-diiodo-2,3-di (4-i-pentylsulfanylphenyl) thieno [3,4-b] pyrazine 40 ml of dimethylformamide synthesized in Example 6 in a 50 ml three-necked flask 2 , 3-di (4-i-pentylsulfanylphenyl) thieno [3,4-b] pyrazine (0.45 g, 0.9 mmol) was added and cooled in an ice bath. N-iodosuccinimide (0.92 g, 4.1 mmol, 4.5 eq.) Was added, and the mixture was stirred in an ice bath for 1 hour and at room temperature for 20 hours. The mixture was cooled in an ice bath and charged with 100 ml of ethyl acetate and 100 ml of a saturated aqueous ammonium chloride solution. The organic layer was separated, the aqueous layer was extracted twice with 50 ml of ethyl acetate, the organic layers were combined, and washed successively with 100 ml of saturated aqueous ammonium chloride solution and 100 ml of saturated brine. Dehydration, filtration, and evaporation were performed with magnesium sulfate, and 0.67 g of a black solid was obtained. The orange fraction of Rf = 0.6 was fractionated by column chromatography (silica gel 100 g, chloroform: hexane = 1: 1 1.0 L) to obtain 0.59 g of an orange solid. Further purification by reprecipitation with 3 ml of chloroform / 30 ml of hexane and drying under reduced pressure at 30 ° C. for 16 hours gave a green solid 5,7-diiodo-2,3-di (4-i-pentylsulfanylphenyl) thieno. 0.53 g (yield 76.3%) of [3,4-b] pyrazine was obtained.

The obtained [Compound 20] was subjected to elemental analysis and ¹ H-NMR, ¹³ C-NMR, IR, LC / MS, and TG / DTA measurement in the same manner as in Example 1 or Example 2. The results are shown below. From these results, it was confirmed that [Compound 20] had the structure of the formula (17).

Compound 20 C ₂₈ H ₃₀ I ₂ N ₂ S ₃ molecular weight 744.6

¹ H-NMR (CDCl ₃ , 300 MHz):
0.92 (12H, d, _JH-H = 6.6 Hz), 1.54 (4H, m), 1.73 (2H, m), 2.93 (4H, t, 7.8 Hz), 7 .23 (4H, dd, _JH-H = 6.9 Hz, _JH-H = 1.8 Hz), 7.44 (4H, dd, _JH-H = 8.7 Hz, _JH-H = 1. 8Hz),
¹³ C-NMR (CDCl ₃ , 75.45 MHz):
22.3, 27.5, 30.7, 37.8, 74.9, 127.1, 130.4, 134.9, 139.8, 143.5, 153.7
IR (KBr):
2950 (s), 2920, 2863, 1589 (s), 1484, 1466, 1384, 1367, 1284 (m), 1263 (m), 1190 (w), 1097 (vs), 1012 (m), 979, 958 , 833 (m), 819, 727, 622, 611, 545, 511 (s)
LC-MS: m / z = 744.93 (APCI +)
m. p. 184.7 ° C

Example 10
[Compound 33] 2,3-Di {4- (p-trifluoromethylphenyl) sulfanylphenyl} -5,7-diiodhieno [3,4-b] pyrazine 2,3 synthesized in Example 8 in a 50 ml flask -Di (4- (p-trifluoromethylphenyl) sulfanylphenylthieno [3,4-b] pyrazine (0.28 g) and DMF (25 ml) were added, and 0.22 g (1.0 mmol) of N-iodosuccinimide was added in an ice bath. The mixture was stirred at room temperature for 18 hours, and 0.12 g (0.52 mmol) of N-iodosuccinimide was added, followed by stirring at room temperature for 24 hours. The reaction solution was put into a mixed solution of 50 ml of an aqueous ammonium solution, the organic layer was separated, and the aqueous layer was extracted three times with 30 ml of toluene. Washing was successively performed with 100 ml of an aqueous solution of ammonium chloride three times and once with 100 ml of tap water, dehydrated with magnesium sulfate and filtered, and the filtrate was concentrated with an evaporator to obtain 0.3 g of a brown solid. The yellow fraction of Rf = 0.3 was fractionated by silica gel chromatography (chloroform: hexane = 1: 2) to obtain a yellow solid, which was further purified by reprecipitation with chloroform and hexane as a yellow solid. 0.15 g (yield 38.5%) of 2,3-di {4- (p-trifluoromethylphenyl) sulfanylphenyl} -5,7-diiodothieno [3,4-b] pyrazine was obtained.

Elemental analysis and ¹ H-NMR, ¹³ C-NMR, ¹⁹ F-NMR, IR, LC / MS, and TG / DTA were measured for the obtained [Compound 33] in the same manner as in Example 1 or Example 3. It was. The results are shown below. From these results, it was confirmed that [Compound 33] had the structure of the formula (18).

¹ H NMR (CDCl ₃ , 300 MHz) δ (ppm):
7.36 (8H, m), 7.49 (4H, m), 7.53 (4H, m)
¹³ C NMR (CDCl ₃ , 75.45 MHz) δ (ppm):
75.64, 118.5, 122.1, 125.7, 125.9, 126.0, 126.1, 126.1, 128.4, 128.8, 129.2, 129.3, 129. 7, 130.0, 131.0, 131.5, 135.9, 137.5, 140.7, 143.6, 153.2
¹⁹ F NMR (CDCl ₃ , 300 MHz) δ (ppm):
(6F, s)
IR (KBr) (cm ⁻¹ ):
1606 (w), 1589, 1402 (w), 1326 (vs), 1282, 1166, 1126 (m), 1106 (w), 1085 (m), 1062 (m), 1014 (m), 979, 958, 827 (m), 613,511
LC-MS m / z = 892.60 (APCI +)
m. p. : 174.8 ° C

(Comparative Example 1)
[Comparative Compound 1-a] Synthesis of 1,2-di (4-isopentyloxyphenyl) ethanedione In a 300 ml four-necked flask, 5.0 g (20.6 mmol) of p-dihydroxybenzyl and 6.86 g of isoamyl bromide (45 .4 mmol, 2.2 eq.), Tetrabutylammonium bromide 3.32 g (10.3 mmol, 0.5 eq.), Potassium carbonate 6.27 g (45.4 mmol, 2.2 eq.) And DMF 150 ml were charged at 120 ° C. For 2 hours. Thereafter, 0.62 g (4.1 mmol, 0.2 eq.) Of isoamyl bromide and 0.57 g (4.1 mmol, 0.2 eq.) Of potassium carbonate were added and stirred for 30 minutes. Further, 0.62 g (4.1 mmol, 0.2 eq.) Of isoamyl bromide and 0.57 g (4.1 mmol, 0.2 eq.) Of potassium carbonate were added and stirred for 1 hour. After cooling to room temperature, 150 ml of water and 150 ml of toluene were added to extract the organic layer. The aqueous layer was extracted twice with 100 ml of toluene, and the organic layers were combined and washed twice with 200 ml of saturated aqueous ammonium chloride solution and twice with 200 ml of water. Magnesium sulfate was added for dehydration, filtered, and then concentrated by an evaporator to obtain a yellow liquid. The obtained yellow liquid was applied to a silica gel column (ethyl acetate / hexane = 1/10 → 1/5) to fractionate a yellow fraction having an Rf value of 0.4. The fraction collected was recrystallized from methanol and washed with cold methanol at 10 ° C. or lower. The obtained solid was dried under reduced pressure at 30 ° C. for 16 hours to obtain 6.55 g (yield 83.1%) of a white solid.

The obtained [Comparative Compound 1-a] was subjected to elemental analysis and ¹ H-NMR, ¹³ C-NMR, IR, GC / MS, and TG / DTA) in the same manner as in Example 1 or Example 2. . The results are shown below. From these results, it was confirmed that [Comparative Compound 1-a] has the structure of the formula (19).

Comparative compound 1-a C ₂₄ H ₃₀ O ₄ molecular weight 382.5

¹ H-NMR (CDCl ₃ , 300 MHz):
0.96 (d, 12H, _JH-H = 6.6 Hz), 1.71 (m, 4H), 1.83 (m, 2H), 4.06 (t, 4H, _JH-H = 6 .6 Hz), 6.95 (m, 4H), 7.93 (4H, m)
¹³ C-NMR (CDCl ₃ , 75.45 Hz):
22.5, 25.0, 37.7, 66.8, 114.7, 126.1, 132.3, 164.5, 193.5
IR (KBr):
2964, 2954, 2937 (s), 2910, 2877 (w), 1672, 1604 (vs), 1577 (s), 1508, 1471, 1423, 1386, 1309, 1294 (m), 1253 (vs), 1230 ( s), 1167 (vs), 1120 (w), 1053 (m), 1009 (w), 980 (m), 941 (w), 893 (s), 876 (w), 845 (m), 810, 796 (w), 766 (s), 700 (m), 651, 619 (s), 513 (m)
GC-MS: m / z = 191.0 (100%), 382.0 (0.67%)
m. p. : 57.7 ° C

(Comparative Example 2)
[Comparative Compound 1]
In a 500 ml separable flask, 2.0 g (5.23 mmol) of [Comparative compound 1-a] synthesized in Comparative Example 1 and 200 ml of ethanol were added and stirred for 10 minutes in an ice bath, and then 3,4-diaminothiophene 0 .60 g (5.23 mmol) and 1.80 ml (31.4 mmol, 6.0 eq.) Of acetic acid were added, and the mixture was stirred in an ice bath for 30 minutes and at room temperature for 3 hours. After confirming consumption of the raw material by TLC, the reaction solution was cooled to 5 ° C. in an ice bath, and the precipitate was collected by filtration and washed with 60 ml of ethanol at 10 ° C. or lower. It dried under reduced pressure at 40 degreeC for 16 hours, and obtained 1.89 g and 78.4 g of light green powder 2,3-di (4-iso-pentylphenoxy) thieno [3,4-b] pyrazine.

Comparative compound 1

The obtained [Comparative Compound 1] was subjected to elemental analysis and ¹ H-NMR, ¹³ C-NMR, IR, LC / MS, and TG / DTA) in the same manner as in Example 1 or Example 2. The results are shown below. From these results, it was confirmed that [Comparative Compound 1] has the structure of the formula (20).

Comparative compound 1 C ₂₈ H ₃₂ N ₂ O ₂ S molecular weight 460.6

¹ H-NMR (CDCl ₃ , 300 MHz):
0.96 (d, 12H, _JH-H = 6.3 Hz), 1.68 (q, 4H, _JH-H = 6.3 Hz), 1.84 (m, 2H), 4.06 (t , 4H, _JH-H = 6.6 Hz), 6.83 (m, 4H), 7.37 (4H, m), 7.96 (2H, s)
¹³ C-NMR (CDCl ₃ , 75.45 Hz):
22.6, 25.0, 37.9, 66.4, 114.2, 116.8, 131.1, 131.6, 141.6, 153.1, 159.7
IR (KBr): 3074 (m), 2956 (s), 2871 (m), 1604 (s), 1573 (w), 1512, 1473 (m), 1362 (w), 1313 (m), 1299 (s) ), 1273 (w), 1246 (vs), 1176 (s), 1138, 1113, 1057 (w), 1020, 970 (m), 862 (w), 833 (s), 781 (w), 736 667, 613, 580, 542 (w)
LC-MS: m / z = 461.87 (APCI +)
m. p. : 123.3 ° C

Measurement of UV-Visible Spectroscopy The compounds 1, 3, 16 and 17 obtained in Examples 5 to 8 above and Comparative Compound 1 obtained in Comparative Example 2 were measured under the following measurement conditions.
Measurement Conditions Compounds 1, 3, 17 and Comparative Compound 1 were prepared using chloroform and Compound 16 was prepared using tetrahydrofuran, and each solution was prepared to a concentration of 2.0 mg / 100 ml, and an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation) : UV-1700).

  In FIG. 1, the ultraviolet visible spectrum of the compound 3 of Example 6 and the comparative compound 1 of the comparative example 1 was shown. FIG. 2 shows ultraviolet-visible spectroscopic spectra of the compounds of Examples 5 to 8 and Comparative Example 2. Table 16 shows the maximum absorption wavelength (λmax) and the molar extinction coefficient ε determined from the obtained spectrum.

  The compound 3 of Example 6 and the comparative compound 1 of Comparative Example 2 are the only difference in the binding element to the phenyl group between S and O. You can see the amplification of the extinction coefficient.

  The thienopyrazine derivative of the present invention can be used as a raw material for a low band gap conjugated polymer compound. The conjugated polymer compound using the thienopyrazine derivative of the present invention as a structural unit exhibits a low band gap, and can be used as an effective organic thin-film solar cell by forming a device.

Claims (10)

The following general formula (1):

[In Formula (1), R ¹ and R ² may be the same or different, and are a linear or branched alkyl group or an aryl group optionally having a substituent. ]
A thienopyrazine derivative represented by: ^2. The thienopyrazine derivative according to claim 1, wherein, in the general formula (1), the aryl group of R ¹ and R ^{2 is} a phenyl group which may have a substituent. The thienopyrazine derivative according to claim 1, wherein, in the general formula (1), the alkyl group represented by R ¹ and R ² is a branched alkyl group having 4 to 8 carbon atoms. General formula (2):

[In Formula (2), R ¹ and R ² may be the same or different, and are a linear or branched alkyl group or an aryl group optionally having a substituent. ]
A diphenylethanedione derivative represented by
General formula (4):

The method for producing a thienopyrazine derivative according to claim 1, which is obtained by a reaction with 3,4-diaminothiophene represented by the formula: General formula (8)

[In Formula (8), R ¹ and R ² may be the same or different, and are a linear or branched alkyl group or an aryl group optionally having a substituent, and X ² is A boron atom selected from the group consisting of fluorine, chlorine, bromine and iodine, a boronic acid residue or a boronic acid ester residue obtained by reacting a diol or alcohol with boric acid. ] The halogenated thienopyrazine derivative represented by these. The halogenated thienopyrazine derivative according to claim 5, wherein X ² in formula (8) is iodine. The halogenated thienopyrazine derivative according to claim 5, wherein, in the formula (8), X ² is a boronic acid ester residue obtained by reacting a boronic acid residue or a diol or alcohol with boric acid. The halogenated thienopyrazine derivative according to claim 5, wherein, in the general formula (8), the alkyl group represented by R ¹ and R ² is a branched alkyl group having 4 to 8 carbon atoms. In the general formula (8), halogenated Chienopirajin derivative according to claim 5-7, wherein the aryl groups for R ¹ and R ² are may phenyl group optionally having a substituent. General formula (3):

[In the formula (3), X ¹ is bromine or chlorine. ]
R ¹ —SH and R ² —SH (R ¹ and R ² may be the same or different, and may be a linear or branched alkyl group or substituent. Which is an aryl group which may have a general formula (2):

[In Formula (2), R ¹ and R ² may be the same or different, and are a linear or branched alkyl group or an aryl group optionally having a substituent. ]
The manufacturing method of the diphenylethanedione derivative represented by these.

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