JP2009280515A - Heterocyclic oligomer compound having pentafluorosulfanyl group - Google Patents
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Abstract
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本発明は、ペンタフルオロスルファニル基を有する複素環オリゴマー化合物に関する。ペンタフルオロスルファニル基を有する複素環オリゴマー化合物は、例えば、電子ペーパーや情報タグ等に適用できる、有機半導体材料として有用な化合物である。 The present invention relates to a heterocyclic oligomer compound having a pentafluorosulfanyl group. A heterocyclic oligomer compound having a pentafluorosulfanyl group is a compound useful as an organic semiconductor material that can be applied to, for example, electronic paper and information tags.
従来、電子をキャリアとする種々の有機半導体材料が検討されており、例えば、ペンタセンやアルキル基を有するチオフェンオリゴマーが開示されている（例えば、非特許文献１参照）。
しかしながら、依然として、より高機能性の半導体の創出が要望されている。
However, there is still a demand for creation of a semiconductor with higher functionality.
本発明の課題は、電子の安定性や移動度が高く、大気中で安定なペンタフルオロスルファニル基を有する複素環オリゴマー化合物及びその製造方法を提供することにある。 An object of the present invention is to provide a heterocyclic oligomer compound having a pentafluorosulfanyl group having high electron stability and mobility and stable in the air, and a method for producing the same.
本発明の課題は、ペンタフルオロスルファニル基を有する複素環オリゴマー化合物によって解決される。 The object of the present invention is solved by a heterocyclic oligomer compound having a pentafluorosulfanyl group.
本発明により、電子ペーパーや情報タグ等に適用できる、有機半導体材料として有用なペンタフルオロスルファニル基を有する複素環オリゴマー化合物を提供することができる。 According to the present invention, a heterocyclic oligomer compound having a pentafluorosulfanyl group useful as an organic semiconductor material that can be applied to electronic paper, information tags, and the like can be provided.
本発明のペンタフルオロスルファニル基を有する複素環オリゴマー化合物は、例えば、チオフェン、ピロール、フラン等の複素環式化合物のオリゴマーに、ペンタフルオロスルファニル基が直接結合した又はフェニル基を介してペンタフルオロスルファニル基が結合した（即ち、ペンタフルオロスルファニルフェニル基が結合している）化合物を示す。その中でも、特に、一般式（１） The heterocyclic oligomer compound having a pentafluorosulfanyl group of the present invention is, for example, a pentafluorosulfanyl group bonded directly to an oligomer of a heterocyclic compound such as thiophene, pyrrole, furan or the like via a phenyl group. Represents a compound to which is bound (ie, a pentafluorosulfanylphenyl group is bound). Among them, in particular, the general formula (1)
ペンタフルオロスルファニル基を有するチオフェンオリゴマー化合物が好適に使用される。以下、複素環式化合物をチオフェンとして説明するが、これらの方法や化合物は、ピロールやフランにも適用が可能である。 A thiophene oligomer compound having a pentafluorosulfanyl group is preferably used. Hereinafter, although a heterocyclic compound is demonstrated as a thiophene, these methods and compounds are applicable also to pyrrole and furan.
ペンタフルオロスルファニル基を有するチオフェンオリゴマー化合物は、前記の一般式（１）で示される。その一般式（１）において、Ｒは、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等の炭素数１〜６のアルキル基（なお、これらの基は、各種異性体を含む。）又はペンタフルオロスルファニルフェニル基を示し、ｎは、２〜４の整数を示す。なお、ペンタフルオロスルファニルフェニル基中のペンタフルオロスルファニル基の位置は特に限定されず、フェニル基上の任意の水素原子は、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる）で置換されていても良い。 The thiophene oligomer compound having a pentafluorosulfanyl group is represented by the general formula (1). In the general formula (1), R is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group (note that these groups represent various isomers. Or a pentafluorosulfanylphenyl group, and n represents an integer of 2 to 4. The position of the pentafluorosulfanyl group in the pentafluorosulfanylphenyl group is not particularly limited, and an arbitrary hydrogen atom on the phenyl group includes a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). ) May be substituted.
前記ペンタフルオロスルファニル基を有するチオフェンオリゴマー化合物の具体例としては、例えば、以下の（１ａ）から（４ｂ）で示される化合物が挙げられる。 Specific examples of the thiophene oligomer compound having a pentafluorosulfanyl group include compounds represented by the following (1a) to (4b).
化合物（１ａ）から（４ｂ）は、いずれもハロゲノペンタフルオロスルファニルベンゼン（例えば、４−ブロモペンタフルオロスルファニルベンゼン（５））を出発原料として合成が可能である。具体的には、例えば、パラジウム化合物の存在下、ハロゲノペンタフルオロスルファニルベンゼン化合物とチオフェンボロン酸エステル化合物とを反応させて、チオフェニルペンタフルオロスルファニルベンゼン化合物を合成する方法；塩化アルミニウムの存在下、ハロゲノチオフェン化合物とチオフェン化合物とをカップリング反応させて炭素−炭素結合を合成する方法；ハロゲン化剤とチオフェンとを反応させてハロゲノチオフェン化合物を合成する方法；リチオ化剤とチオフェンとを反応させてチオフェンをリチオ化した後、ボロン酸エステル化合物と反応させてチオフェンボロン酸エステル化合物を合成する方法（例えば、鈴木カップリング）；パラジウム化合物及びスズ化合物の存在下、ハロゲノチオフェン化合物をカップリング反応させて多量体を合成する方法；ハロゲノチオフェンとマグネシウム金属とを反応させてグリニャール試薬を合成した後、ハロゲノチオフェン化合物をカップリング反応させて多量体を合成する方法（例えば、熊田・玉尾カップリング）等の方法を適宜組み合わせることにより合成される。なお、それぞれ使用する原料については、市販品又は合成品を使用することができ、必要に応じて脱水、脱気等の前処理を行う。 Compounds (1a) to (4b) can all be synthesized using halogenopentafluorosulfanylbenzene (for example, 4-bromopentafluorosulfanylbenzene (5)) as a starting material. Specifically, for example, a method of synthesizing a thiophenylpentafluorosulfanylbenzene compound by reacting a halogenopentafluorosulfanylbenzene compound with a thiophene boronic ester compound in the presence of a palladium compound; A method of synthesizing a carbon-carbon bond by coupling a thiophene compound and a thiophene compound; a method of synthesizing a halogenothiophene compound by reacting a halogenating agent and thiophene; a reaction of a lithiating agent and thiophene to thiophene A method of synthesizing a thiophene boronate ester compound by reacting with a boronate ester compound after lithiation (for example, Suzuki coupling); coupling a halogenothiophene compound in the presence of a palladium compound and a tin compound A method of synthesizing a multimer; a method in which a halogenothiophene is reacted with magnesium metal to synthesize a Grignard reagent, and then a halogenothiophene compound is coupled to synthesize a multimer (for example, Kumada / Tamao Cup) (Ring) and the like, which are combined by appropriate combination. In addition, about the raw material to each use, a commercial item or a synthetic product can be used, and pre-processing, such as dehydration and deaeration, is performed as needed.
化合物（１ａ）は、例えば、以下のルートで合成できる。 Compound (1a) can be synthesized, for example, by the following route.
化合物（１ｂ）は、例えば、以下のルートで合成できる。 Compound (1b) can be synthesized, for example, by the following route.
化合物（２）は、例えば、以下のルートで合成できる。 Compound (2) can be synthesized, for example, by the following route.
化合物（３）は、例えば、以下のルートで合成できる。 Compound (3) can be synthesized, for example, by the following route.
化合物（４ａ）は、例えば、以下のルートで合成できる。 Compound (4a) can be synthesized, for example, by the following route.
次に、実施例を挙げて本発明を具体的に説明するが、本発明の範囲はこれらに限定されるものではない。 Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.
実施例１（化合物（７）；２−（４−ペンタフルオロスルファニルフェニル）チオフェンの合成）
４−ブロモペンタフルオロスルファニルベンゼン（５）０．８４８ｇ（３．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム９８．２ｍｇ（０．０８５ｍｍｏｌ）、炭酸ナトリウム０．６３６ｇ（６．０ｍｍｏｌ）、トルエン９ｍｌ、水６ｍｌ、エタノール９ｍｌ及び２−チオフェンボロン酸ネオペンチルグリコールエステル（６）０．４９０ｇ（２．５ｍｍｏｌ）を混合して室温で１３．５時間反応させ、無色鱗片状結晶として、２−（４−ペンタフルオロスルファニルフェニル）チオフェン０．４９４ｇを得た（単離収率；５８％）。
Example 1 (Compound (7); Synthesis of 2- (4-pentafluorosulfanylphenyl) thiophene)
4-Bromopentafluorosulfanylbenzene (5) 0.848 g (3.0 mmol), tetrakis (triphenylphosphine) palladium 98.2 mg (0.085 mmol), sodium carbonate 0.636 g (6.0 mmol), toluene 9 ml, water 6 ml, ethanol 9 ml and 2-thiopheneboronic acid neopentyl glycol ester (6) 0.490 g (2.5 mmol) were mixed and reacted at room temperature for 13.5 hours to give 2- (4-penta) as colorless scaly crystals. 0.494 g of fluorosulfanylphenyl) thiophene was obtained (isolation yield; 58%).
融点；１４３〜１４４℃
1HNMR(CDCl3,500MHz)δ(ppm)=7.74〜7.76(2H,m,Ar-H),7.67(2H,d,J=8.3Hz,Ar-H),7.37〜7.40(2H,m, Ar-H),7.11〜7.13(1H,m, Ar-H)
Melting point: 143-144 ° C
1 HNMR (CDCl 3 , 500 MHz) δ (ppm) = 7.74 to 7.76 (2H, m, Ar-H), 7.67 (2H, d, J = 8.3Hz, Ar-H), 7.37 to 7.40 (2H, m, Ar-H), 7.11 to 7.13 (1H, m, Ar-H)
実施例２−１（化合物（８）；２−クロロ−５−（４−ペンタフルオロスルファニルフェニル）チオフェンの合成）
化合物（７）０．４２６ｇ（１．４９ｍｍｏｌ）、Ｎ−クロロスクシンイミド０．１９９ｇ（１．４９ｍｍｏｌ）及びＮ，Ｎ−ジメチルホルムアミド３ｍｌを混合して５０〜６０℃で３時間反応させ、無色鱗片状結晶として、２−クロロ−５−（４−ペンタフルオロスルファニルフェニル）チオフェン０．３２ｇを得た（単離収率；６７％）。
Example 2-1 (Compound (8); Synthesis of 2-chloro-5- (4-pentafluorosulfanylphenyl) thiophene)
Compound (7) 0.426 g (1.49 mmol), N-chlorosuccinimide 0.199 g (1.49 mmol) and N, N-dimethylformamide 3 ml were mixed and reacted at 50-60 ° C. for 3 hours to give colorless flakes. As a crystal, 0.32 g of 2-chloro-5- (4-pentafluorosulfanylphenyl) thiophene was obtained (isolation yield; 67%).
1HNMR(CDCl3,500MHz)δ(ppm)=7.74〜7.76(2H,m,Ar-H),7.56(2H,d,J=9.0Hz,Ar-H),7.16(1H,d,J= 4.2Hz,Ar-H),6.93〜6.94(1H,m, Ar-H) 1 HNMR (CDCl 3 , 500 MHz) δ (ppm) = 7.74-7.76 (2H, m, Ar-H), 7.56 (2H, d, J = 9.0 Hz, Ar-H), 7.16 (1H, d, J = 4.2Hz, Ar-H), 6.93-6.94 (1H, m, Ar-H)
実施例２−２（化合物（８）；２−クロロ−５−（４−ペンタフルオロスルファニルフェニル）チオフェンの合成）
４−ブロモペンタフルオロスルファニルベンゼン（５）０．８４９ｇ（３．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム９８．２ｍｇ（０．０８５ｍｍｏｌ）、炭酸ナトリウム０．６３６ｇ（６．０ｍｍｏｌ）、トルエン９ｍｌ、水６ｍｌ、エタノール９ｍｌ及び２−クロロ−５−チオフェンボロン酸ネオペンンチルグリコールエステル（９）０．５７６ｇ（２．５ｍｍｏｌ）を混合して還流させながら８時間反応させ、無色鱗片状結晶として、２−クロロ−５−（４−ペンタフルオロスルファニルフェニル）チオフェン０．３５０ｇを得た（単離収率；４４％）。
Example 2-2 (Compound (8); Synthesis of 2-chloro-5- (4-pentafluorosulfanylphenyl) thiophene)
4-bromopentafluorosulfanylbenzene (5) 0.849 g (3.0 mmol), tetrakis (triphenylphosphine) palladium 98.2 mg (0.085 mmol), sodium carbonate 0.636 g (6.0 mmol), toluene 9 ml, water 6 ml, ethanol 9 ml and 2-chloro-5-thiopheneboronic acid neopentyl glycol ester (9) 0.576 g (2.5 mmol) were mixed and reacted for 8 hours while refluxing to give colorless scaly crystals as 2 0.350 g of -chloro-5- (4-pentafluorosulfanylphenyl) thiophene was obtained (isolation yield; 44%).
融点；９７〜９８℃ Melting point: 97-98 ° C
実施例３（化合物（１ａ）；２−（４−ペンタフルオロスルファニルフェニル）−５−（５−（４−ペンタフルオロスルファニルフェニル）チオフェン−２−イル）チオフェンの合成）
テトラキス（トリフェニルホスフィン）パラジウム１８．４ｍｇ（０．１５９ｍｍｏｌ）、化合物（８）０．３ｇ（０．９３５ｍｍｏｌ）、ヘキサブチルジチン０．３２６ｇ（０．５６１ｍｍｏｌ）及びトルエン４ｍｌを混合して還流させながら９時間反応させ、黄色針状結晶として、２−（４−ペンタフルオロスルファニルフェニル）−５−（５−（４−ペンタフルオロスルファニルフェニル）チオフェン−２−イル）チオフェン０．０３８ｇを得た（単離収率；２０％）。
Example 3 (Compound (1a); Synthesis of 2- (4-pentafluorosulfanylphenyl) -5- (5- (4-pentafluorosulfanylphenyl) thiophen-2-yl) thiophene)
Tetrakis (triphenylphosphine) palladium 18.4 mg (0.159 mmol), compound (8) 0.3 g (0.935 mmol), hexabutylditine 0.326 g (0.561 mmol) and toluene 4 ml were mixed and refluxed. The reaction was conducted for 9 hours to obtain 0.038 g of 2- (4-pentafluorosulfanylphenyl) -5- (5- (4-pentafluorosulfanylphenyl) thiophen-2-yl) thiophene as yellow needle-like crystals ( Isolation yield; 20%).
融点；３０８〜３０９℃
1HNMR(CDCl3,500MHz)δ(ppm)=7.76〜7.78(4H,m,Ar-H),7.65(4H,d,J=9.0Hz,Ar-H),7.32(2H,d,J=3.9 Hz,Ar-H),7.22(2H,d, J=3.7 Hz,Ar-H)
Melting point: 308-309 ° C
1 HNMR (CDCl 3 , 500 MHz) δ (ppm) = 7.76 to 7.78 (4H, m, Ar-H), 7.65 (4H, d, J = 9.0 Hz, Ar-H), 7.32 (2H, d, J = 3.9 Hz, Ar-H), 7.22 (2H, d, J = 3.7 Hz, Ar-H)
実施例４（化合物（１１）；２−クロロ−５−（チオフェン−２−イル）チオフェンの合成）
２−クロロチオフェン（１０）８．３０ｇ（７０ｍｍｏｌ）、塩化アルミニウム９．３３ｇ（７０ｍｍｏｌ）及びジクロロメタン１４０ｍｌを混合して還流させながら１．５時間反応させ、薄黄色鱗片状結晶として、２−クロロ−５−（チオフェン−２−イル）チオフェン５．３２２ｇを得た（単離収率；７６％）。
Example 4 (Compound (11); Synthesis of 2-chloro-5- (thiophen-2-yl) thiophene)
A mixture of 8.30 g (70 mmol) of 2-chlorothiophene (10), 9.33 g (70 mmol) of aluminum chloride and 140 ml of dichloromethane was reacted under reflux for 1.5 hours to give 2-chloro- 5.322 g of 5- (thiophen-2-yl) thiophene was obtained (isolation yield; 76%).
融点；３０〜３１℃
1HNMR(CDCl3,200MHz)δ(ppm)=7.22(1H,dd,J1=5.1Hz,J2=1.1Hz,Ar-H),7.10(1H,dd, J1=3.7Hz,J2=1.1Hz,Ar-H),6.98〜7.03(1H,m,Ar-H),6.93(1H,d,J=3.8Hz,Ar-H),6.83(1H,d, J=3.8Hz, Ar-H)
Melting point: 30-31 ° C
1 HNMR (CDCl 3 , 200 MHz) δ (ppm) = 7.22 (1H, dd, J 1 = 5.1 Hz, J 2 = 1.1 Hz, Ar-H), 7.10 (1H, dd, J 1 = 3.7 Hz, J 2 = 1.1Hz, Ar-H), 6.98 to 7.03 (1H, m, Ar-H), 6.93 (1H, d, J = 3.8Hz, Ar-H), 6.83 (1H, d, J = 3.8Hz, Ar -H)
実施例５（化合物（１４）；２−（５−クロロチオフェン−２−イル）チオフェン−５−ボロン酸ネオペンチルグリコールエステルの合成）
１．６ｍｏｌ／ｌのｎ−ブチルリチウム１７．９７ｍｌ（２８．８ｍｍｏｌ）、ジイソプロピルアミン２．５２９ｇ（２５ｍｍｏｌ）及び乾燥テトラヒドロフラン２０ｍｌを混合し−７８℃にて攪拌させた。次いで、化合物（１１）５．０１８ｇ（２５ｍｍｏｌ）の乾燥テトラヒドロフラン（５ｍｌ）溶液を滴下し、同温度で１時間、−４０℃で１時間反応させた。その後、−７８℃まで冷却し、ホウ酸トリ（ｎ−ブチル）８．０５５ｇ（３５ｍｍｏｌ）の乾燥テトラヒドロフラン（７ｍｌ）溶液を滴下し、同温度で２．５時間、室温で１晩反応させた。得られた反応液を２ｍｏｌ／ｌ塩酸２５ｍｌで処理し、２，２−ジメチル−１，３−プロパンジオール２．６０４ｇ（２５ｍｍｏｌ）を加えて反応させ、茶色粉末状結晶として、２−（５−クロロチオフェン−２−イル）チオフェン−５−ボロン酸ネオペンチルグリコールエステル４．８９５ｇを得た（単離収率；６３％）。
Example 5 (Compound (14); Synthesis of 2- (5-chlorothiophen-2-yl) thiophene-5-boronic acid neopentyl glycol ester)
1.6 mol / l n-butyllithium 17.97 ml (28.8 mmol), diisopropylamine 2.529 g (25 mmol) and
融点；１１２．５〜１１３．５℃
1HNMR(CDCl3,200MHz)δ(ppm)=7.44(1H,d,J=3.5Hz,Ar-H),7.14(1H,d,J=3.7Hz,Ar-H),6.97(1H,d,J=4.0Hz,Ar-H),6.83(1H,d,J=3.5Hz,Ar-H),3.76(4H,s,-CH2-),1.03(6H,s,-CH3)
Melting point: 112.5-113.5 ° C
1 HNMR (CDCl 3 , 200MHz) δ (ppm) = 7.44 (1H, d, J = 3.5Hz, Ar-H), 7.14 (1H, d, J = 3.7Hz, Ar-H), 6.97 (1H, d , J = 4.0Hz, Ar-H), 6.83 (1H, d, J = 3.5Hz, Ar-H), 3.76 (4H, s, -CH 2- ), 1.03 (6H, s, -CH 3 )
実施例６（化合物（１５）；２−（５−クロロチオフェン−２−イル）チオフェン−５−（４−ペンタフルオロスルファニルフェニル）チオフェンの合成）
化合物（５）１．１３２ｇ（４．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム０．１３１ｇ（０．１１３ｍｍｏｌ）、炭酸ナトリウム０．８４８ｇ（７．９９ｍｍｏｌ）、トルエン１２ｍｌ、水８ｍｌ、エタノール１２ｍｌ及び化合物（１４）１．０４１ｇ（３．３３ｍｍｏｌ）を混合して還流させながら６時間反応させ、黄色粉末状結晶として、２−（５−クロロチオフェン−２−イル）チオフェン−５−（４−ペンタフルオロスルファニルフェニル）チオフェン０．９６３ｇを得た（単離収率；７２％）。
Example 6 (Compound (15); Synthesis of 2- (5-chlorothiophen-2-yl) thiophene-5- (4-pentafluorosulfanylphenyl) thiophene)
Compound (5) 1.132 g (4.0 mmol), tetrakis (triphenylphosphine) palladium 0.131 g (0.113 mmol), sodium carbonate 0.848 g (7.99 mmol), toluene 12 ml, water 8 ml, ethanol 12 ml and compound (14) 1.041 g (3.33 mmol) was mixed and allowed to react for 6 hours under reflux to give 2- (5-chlorothiophen-2-yl) thiophen-5- (4-pentafluoro) as yellow powdery crystals. 0.963 g of (sulfanylphenyl) thiophene was obtained (isolation yield; 72%).
融点；１４８〜１４９ｇ
1HNMR(CDCl3,200MHz)δ(ppm)=7.40〜7.85(2H,m,Ar-H),7.63(2H,d,J=8.9Hz,Ar-H),7.30(1H,d, J=3.8 Hz,Ar-H),7.10(1H,d,J=3.8Hz,Ar-H),6.99(1H,d, J=3.8Hz, Ar-H), 6.87(1H,d, J=3.8Hz, Ar-H)
Melting point: 148-149g
1 HNMR (CDCl 3 , 200 MHz) δ (ppm) = 7.40-7.85 (2H, m, Ar-H), 7.63 (2H, d, J = 8.9Hz, Ar-H), 7.30 (1H, d, J = 3.8 Hz, Ar-H), 7.10 (1H, d, J = 3.8Hz, Ar-H), 6.99 (1H, d, J = 3.8Hz, Ar-H), 6.87 (1H, d, J = 3.8Hz , Ar-H)
実施例７（化合物（１ｂ）；２−（５−（４−ペンタフルオロスルファニルフェニル）チオフェン−２−イル）−５−（５−（４−ペンタフルオロスルファニルフェニル）チオフェン−２−イル）チオフェン−２−イル）チオフェンの合成）
テトラキス（トリフェニルホスフィン）パラジウム１９．６ｍｇ（０．０１７ｍｍｏｌ）、化合物（１５）０．４０３ｇ（１．０ｍｍｏｌ）、ヘキサブチルジチン０．３４８ｇ（０．６ｍｍｏｌ）及びトルエン４．３ｍｌを混合して還流させながら１２時間反応させ、茶色粉末状結晶として、２−（５−（４−ペンタフルオロスルファニルフェニル）チオフェン−２−イル）−５−（５−（４−ペンタフルオロスルファニル）チオフェン−２−イル）チオフェン−２−イル）チオフェン０．０６７ｇを得た（単離収率；１８％）。
Example 7 (compound (1b); 2- (5- (4-pentafluorosulfanylphenyl) thiophen-2-yl) -5- (5- (4-pentafluorosulfanylphenyl) thiophen-2-yl) thiophene- Synthesis of 2-yl) thiophene)
Tetrakis (triphenylphosphine) palladium 19.6 mg (0.017 mmol), compound (15) 0.403 g (1.0 mmol), hexabutylditine 0.348 g (0.6 mmol) and toluene 4.3 ml were mixed. The mixture was allowed to react for 12 hours while refluxing to give 2- (5- (4-pentafluorosulfanylphenyl) thiophen-2-yl) -5- (5- (4-pentafluorosulfanyl) thiophen-2-yl as brown powdery crystals. Ir) 0.067 g of thiophen-2-yl) thiophene was obtained (isolation yield; 18%).
融点；３００℃以上 Melting point: 300 ° C or higher
実施例８（化合物（１７）；２−（５−クロロチオフェン−２−イル）チオフェン−５−（３−ペンタフルオロスルファニルフェニル）チオフェンの合成）
３−ブロモペンタフルオロスルファニルベンゼン（１６）１．６９８ｇ（６．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム０．１９６ｇ（０．１７ｍｍｏｌ）、炭酸ナトリウム１．２７２ｇ（１２．０ｍｍｏｌ）、トルエン１８ｍｌ、水３．６ｍｌ、エタノール１８ｍｌ及び化合物（１４）１．５６３ｇ（５．０ｍｍｏｌ）を混合して還流させながら６時間反応させ、薄黄色粉末状結晶として、２−（５−クロロチオフェン−２−イル）チオフェン−５−（３−ペンタフルオロスルファニルフェニル）チオフェン１．３６５ｇを得た（単離収率；６８％）。
Example 8 (Compound (17); Synthesis of 2- (5-chlorothiophen-2-yl) thiophene-5- (3-pentafluorosulfanylphenyl) thiophene)
3-bromopentafluorosulfanylbenzene (16) 1.698 g (6.0 mmol), tetrakis (triphenylphosphine) palladium 0.196 g (0.17 mmol), sodium carbonate 1.272 g (12.0 mmol), toluene 18 ml, water 3.6 ml, 18 ml of ethanol and 1.563 g (5.0 mmol) of compound (14) were mixed and reacted for 6 hours under reflux to give 2- (5-chlorothiophen-2-yl) as light yellow powdery crystals. 1.365 g of thiophen-5- (3-pentafluorosulfanylphenyl) thiophene was obtained (isolation yield; 68%).
融点；８７．５〜８８．５℃
1HNMR(CDCl3,200MHz)δ(ppm)=7.94(1H,t,J=1.8Hz,Ar-H),7.64〜7.72(2H,m,Ar-H),7.44〜7.52(1H,m,Ar-H),7.27(1H,d,J=3.8Hz,Ar-H),7.09(1H,d,J=3.8Hz,Ar-H),6.99(1H,d, J=3.8Hz, Ar-H), 6.86(1H,d, J=3.8Hz, Ar-H)
Melting point: 87.5-88.5 ° C
1 HNMR (CDCl 3 , 200 MHz) δ (ppm) = 7.94 (1H, t, J = 1.8 Hz, Ar-H), 7.64 to 7.72 (2H, m, Ar-H), 7.44 to 7.52 (1H, m, Ar-H), 7.27 (1H, d, J = 3.8Hz, Ar-H), 7.09 (1H, d, J = 3.8Hz, Ar-H), 6.99 (1H, d, J = 3.8Hz, Ar- H), 6.86 (1H, d, J = 3.8Hz, Ar-H)
実施例９（化合物（２）；２−（５−（３−ペンタフルオロスルファニルフェニル）チオフェン−２−イル）−５−（５−（３−ペンタフルオロスルファニルフェニル）チオフェン−２−イル）チオフェン−２−イル）チオフェンの合成）
テトラキス（トリフェニルホスフィン）パラジウム２９．５ｍｇ（０．０２５５ｍｍｏｌ）、化合物（１７）０．６０４ｇ（１．５ｍｍｏｌ）、ヘキサブチルジチン０．８７０ｇ（１．５ｍｍｏｌ）及びトルエン６．０ｍｌを混合して還流させながら１２時間反応させ、橙色鱗片状結晶として、２−（５−（３−ペンタフルオロスルファニルフェニル）チオフェン−２−イル）−５−（５−（３−ペンタフルオロスルファニルフェニル）チオフェン−２−イル）チオフェン−２−イル）チオフェン０．０４０ｇを得た（単離収率；７％）。
Example 9 (compound (2); 2- (5- (3-pentafluorosulfanylphenyl) thiophen-2-yl) -5- (5- (3-pentafluorosulfanylphenyl) thiophen-2-yl) thiophene- Synthesis of 2-yl) thiophene)
Tetrakis (triphenylphosphine) palladium 29.5 mg (0.0255 mmol), compound (17) 0.604 g (1.5 mmol), hexabutylditine 0.870 g (1.5 mmol) and toluene 6.0 ml were mixed. The reaction was carried out for 12 hours while refluxing, and 2- (5- (3-pentafluorosulfanylphenyl) thiophen-2-yl) -5- (5- (3-pentafluorosulfanylphenyl) thiophene-2 was obtained as orange scaly crystals. 0.04 g of yl) thiophen-2-yl) thiophene was obtained (isolation yield; 7%).
融点；２２９〜２３０℃
1HNMR(CDCl3,500MHz)δ(ppm)=7.96(2H,t,J=1.9Hz,Ar-H),7.70(2H,d,J=7.6Hz,Ar-H),7.65〜7.67(2H,m,Ar-H),7.47(2H,t,J=8.5Hz,Ar-H),7.28(2H,d,J=3.7Hz,Ar-H),7.17(2H,d, J=3.7Hz, Ar-H), 7.14(2H,d, J=3.9Hz, Ar-H),7.12(2H,d, J=3.9Hz, Ar-H)
Melting point: 229-230 ° C
1 HNMR (CDCl 3 , 500 MHz) δ (ppm) = 7.96 (2H, t, J = 1.9Hz, Ar-H), 7.70 (2H, d, J = 7.6Hz, Ar-H), 7.65 to 7.67 (2H , m, Ar-H), 7.47 (2H, t, J = 8.5Hz, Ar-H), 7.28 (2H, d, J = 3.7Hz, Ar-H), 7.17 (2H, d, J = 3.7Hz , Ar-H), 7.14 (2H, d, J = 3.9Hz, Ar-H), 7.12 (2H, d, J = 3.9Hz, Ar-H)
実施例１０（化合物（３）；２−ヘキシル−（５−（５−（４−ペンタフルオロスルファニルフェニル）チオフェン−２−イル）チオフェン−２−イル）チオフェンの合成）
乾燥させたマグネシウム４０．１ｍｇ（１．６５ｍｍｏｌ）、乾燥させたエーテル２．２５ｍｌ及び２−ブロモ−５−ヘキシルチオフェン（１９）０．３７１ｇ（１．５０ｍｍｏｌ）を混合して３５℃で攪拌させながらグリニャール試薬を合成した。次いで、ジクロロ（１，１’−ジフェニルホスフィノフェロセン）パラジウム８．１６ｍｇ（０．０１ｍｍｏｌ）、化合物（１５）０．４０３ｇ（１．０ｍｍｏｌ）及びトルエン１．０ｍｌを混合して還流させながら２．５時間反応させ、黄色粉末状結晶として、２−ヘキシル−（５−（５−（４−ペンタフルオロスルファニルフェニル）チオフェン−２−イル）チオフェン−２−イル）チオフェン１．４８ｇを得た（単離収率；８９％）。
Example 10 (Compound (3); Synthesis of 2-hexyl- (5- (5- (4-pentafluorosulfanylphenyl) thiophen-2-yl) thiophen-2-yl) thiophene)
While mixing 40.1 mg (1.65 mmol) of dried magnesium, 2.25 ml of dried ether and 0.371 g (1.50 mmol) of 2-bromo-5-hexylthiophene (19), the mixture was stirred at 35 ° C. A Grignard reagent was synthesized. Subsequently, 8.16 mg (0.01 mmol) of dichloro (1,1′-diphenylphosphinoferrocene) palladium, 0.403 g (1.0 mmol) of the compound (15) and 1.0 ml of toluene were mixed and refluxed. The mixture was reacted for 5 hours to obtain 1.48 g of 2-hexyl- (5- (5- (4-pentafluorosulfanylphenyl) thiophen-2-yl) thiophen-2-yl) thiophene as a yellow powdery crystal (single (Separation yield; 89%).
融点；２３５〜２３６℃
1HNMR(CDCl3,500MHz)δ(ppm)=7.75(2H,d,J=8.5Hz,Ar-H),7.64(2H,d,J=8.5Hz,Ar-H),7.31(1H,d,J=3.7Hz,Ar-H),7.15(1H,d,J=3.7Hz,Ar-H),7.11(1H,d,J=3.7Hz,Ar-H),7.02(1H,d, J=3.7Hz, Ar-H), 7.00(1H,d, J=3.4Hz, Ar-H),6.69(1H,d, J=3.4Hz, Ar-H),2.80(2H,t, J=7.3Hz,-CH2-),1.69(2H,q, J=7.6Hz, -CH2-),1.36〜1.40(2H,m, -CH2-),1.32〜1.33(4H,m, -CH2-),0.89(3H,t, J=6.3Hz, -CH3)
Melting point: 235-236 ° C
1 HNMR (CDCl 3 , 500MHz) δ (ppm) = 7.75 (2H, d, J = 8.5Hz, Ar-H), 7.64 (2H, d, J = 8.5Hz, Ar-H), 7.31 (1H, d , J = 3.7Hz, Ar-H), 7.15 (1H, d, J = 3.7Hz, Ar-H), 7.11 (1H, d, J = 3.7Hz, Ar-H), 7.02 (1H, d, J = 3.7Hz, Ar-H), 7.00 (1H, d, J = 3.4Hz, Ar-H), 6.69 (1H, d, J = 3.4Hz, Ar-H), 2.80 (2H, t, J = 7.3 Hz, -CH 2- ), 1.69 (2H, q, J = 7.6Hz, -CH 2- ), 1.36 to 1.40 (2H, m, -CH 2- ), 1.32 to 1.33 (4H, m, -CH 2 -), 0.89 (3H, t, J = 6.3Hz, -CH 3 )
実施例１１（化合物（４ａ）；２−（５−ヘキシルチオフェン−２−イル）−５−（３−ペンタフルオロスルファニルフェニル）チオフェンの合成）
テトラキス（トリフェニルホスフィン）パラジウム５８．９ｍｇ（０．０５１ｍｍｏｌ）、化合物（１６）０．５０９ｇ（１．８ｍｍｏｌ）、炭酸ナトリウム０．３８２ｇ（３．６ｍｍｏｌ）、２−（５−ヘキシルチオフェン−２−イル）−５−ボロン酸ネオペンチルグリコールエステル（１８）０．５４４ｇ（１．５ｍｍｏｌ）、水３．６ｍｌ、エタノール５．４ｍｌ及びトルエン５．４ｍｌを混合して還流させながら１３．５時間反応させ、薄黄色粉末状結晶として、２−（５−ヘキシルチオフェン−２−イル）−５−（３−ペンタフルオロスルファニルフェニル）チオフェン０．５５５ｇを得た（単離収率；８２％）。
Example 11 (Compound (4a); Synthesis of 2- (5-hexylthiophen-2-yl) -5- (3-pentafluorosulfanylphenyl) thiophene)
Tetrakis (triphenylphosphine) palladium 58.9 mg (0.051 mmol), compound (16) 0.509 g (1.8 mmol), sodium carbonate 0.382 g (3.6 mmol), 2- (5-hexylthiophene-2- Yl) -5-boronic acid neopentyl glycol ester (18) 0.544 g (1.5 mmol), water 3.6 ml, ethanol 5.4 ml and toluene 5.4 ml were mixed and reacted for 13.5 hours while refluxing. As a pale yellow powdery crystal, 0.555 g of 2- (5-hexylthiophen-2-yl) -5- (3-pentafluorosulfanylphenyl) thiophene was obtained (isolated yield; 82%).
融点；４８．５〜４９．５℃
1HNMR(CDCl3,500MHz)δ(ppm)=7.93(1H,t,J=2.0Hz,Ar-H),7.69(1H,d,J=7.8Hz,Ar-H),7.64(1H,dd,J1=7.8Hz,J2=1.7Hz,Ar-H),7.46(1H,t,J=8.1Hz,Ar-H),7.26(1H,d,J=3.7Hz,Ar-H),7.09(1H,d,J=3.9Hz,Ar-H), 7.04(1H,d, J=3.4Hz, Ar-H),6.71(1H,d, J=3.7Hz, Ar-H),2.81(2H,t,J=7.6Hz,-CH2-),1.69(2H,q,J=7.3Hz,-CH2-),1.30〜1.54(6H,m,-CH2-),0.90(3H,t, J=4.4Hz, -CH3)
Melting point: 48.5-49.5 ° C
1 HNMR (CDCl 3 , 500MHz) δ (ppm) = 7.93 (1H, t, J = 2.0Hz, Ar-H), 7.69 (1H, d, J = 7.8Hz, Ar-H), 7.64 (1H, dd , J 1 = 7.8Hz, J 2 = 1.7Hz, Ar-H), 7.46 (1H, t, J = 8.1Hz, Ar-H), 7.26 (1H, d, J = 3.7Hz, Ar-H), 7.09 (1H, d, J = 3.9Hz, Ar-H), 7.04 (1H, d, J = 3.4Hz, Ar-H), 6.71 (1H, d, J = 3.7Hz, Ar-H), 2.81 ( 2H, t, J = 7.6Hz, -CH 2 -), 1.69 (2H, q, J = 7.3Hz, -CH 2 -), 1.30~1.54 (6H, m, -CH 2 -), 0.90 (3H, t, J = 4.4Hz, -CH 3 )
実施例１２（化合物（４ｂ）；２−へキシル−５−（５−（３−ペンタフルオロスルファニルフェニル）チオフェン−２−イル）チオフェン−２−イル）チオフェンの合成）
乾燥させたマグネシウム４０．１ｍｇ（１．６５ｍｍｏｌ）、乾燥させたエーテル２．２５ｍｌ及び化合物（１９）０．３７１ｇ（１．５０ｍｍｏｌ）を混合して３５℃で攪拌させながらグリニャール試薬を合成した。次いで、ジクロロ（１，１’−ジフェニルホスフィノフェロセン）パラジウム８．１６ｍｇ（０．０１ｍｍｏｌ）、化合物（１７）０．４０３ｇ（１．０ｍｍｏｌ）及びトルエン１．０ｍｌを混合して還流させながら２．５時間反応させ、黄色鱗片状結晶として、２−へキシル−５−（５−（３−ペンタフルオロスルファニルフェニル）チオフェン−２−イル）チオフェン−２−イル）チオフェン０．４２２ｇを得た（単離収率；７８％）。
Example 12 (Compound (4b); Synthesis of 2-hexyl-5- (5- (3-pentafluorosulfanylphenyl) thiophen-2-yl) thiophen-2-yl) thiophene)
40.1 mg (1.65 mmol) of dried magnesium, 2.25 ml of dried ether and 0.371 g (1.50 mmol) of compound (19) were mixed and a Grignard reagent was synthesized while stirring at 35 ° C. Next, 8.16 mg (0.01 mmol) of dichloro (1,1′-diphenylphosphinoferrocene) palladium, 0.403 g (1.0 mmol) of compound (17) and 1.0 ml of toluene were mixed and refluxed. The reaction was performed for 5 hours to obtain 0.422 g of 2-hexyl-5- (5- (3-pentafluorosulfanylphenyl) thiophen-2-yl) thiophen-2-yl) thiophene as a yellow scaly crystal (single (Separation yield; 78%).
融点；１３０〜１３１℃
1HNMR(CDCl3,500MHz)δ(ppm)=7.94〜7.95(1H,m,Ar-H),7.70(1H,d,J=8.1Hz,Ar-H),7.64〜7.66(1H,m,Ar-H),7.48(1H,t,J=8.1Hz,Ar-H),7.28(1H,d,J=3.9Hz,Ar-H),7.15(1H,d,J=3.9Hz,Ar-H),7.11(1H,d,J=3.9Hz,Ar-H),7.02(1H,d,J=3.9Hz,Ar-H),7.00(1H,d,J=3.7Hz,Ar-H),6.69〜6.70(1H,m,Ar-H),2.80(2H,t,J=7.8Hz,-CH2-),1.69(2H,q,J=7.6Hz,-CH2-),1.30〜1.41(6H,m,-CH2-),0.89〜0.91(3H,m, -CH3)
Melting point: 130-131 ° C
1 HNMR (CDCl 3 , 500 MHz) δ (ppm) = 7.94 to 7.95 (1H, m, Ar-H), 7.70 (1H, d, J = 8.1 Hz, Ar-H), 7.64 to 7.66 (1H, m, Ar-H), 7.48 (1H, t, J = 8.1Hz, Ar-H), 7.28 (1H, d, J = 3.9Hz, Ar-H), 7.15 (1H, d, J = 3.9Hz, Ar- H), 7.11 (1H, d, J = 3.9Hz, Ar-H), 7.02 (1H, d, J = 3.9Hz, Ar-H), 7.00 (1H, d, J = 3.7Hz, Ar-H) , 6.69~6.70 (1H, m, Ar -H), 2.80 (2H, t, J = 7.8Hz, -CH 2 -), 1.69 (2H, q, J = 7.6Hz, -CH 2 -), 1.30~ 1.41 (6H, m, -CH 2- ), 0.89 ~ 0.91 (3H, m, -CH 3 )
なお、ヘキシル基を有する化合物（３）、（４ａ）及び（４ｂ）は、汎用溶媒に高い溶解性（２２００〜１６９０００ｐｐｍ）を示した。又、化合物（３）を用いて電界効果トランジスタ（ＦＥＴ）素子（チャネル長；２０μｍ、チャネル幅；１ｍｍ、膜厚；１１０ｎｍ、トップコンタクト型）を作成して電荷移動度を測定したところ、３．３×１０−３ｃｍ２／Ｖｓと半導体性能を示唆する結果が得られた。 In addition, the compounds (3), (4a) and (4b) having a hexyl group showed high solubility (2200 to 169000 ppm) in a general-purpose solvent. Further, a field effect transistor (FET) element (channel length: 20 μm, channel width: 1 mm, film thickness: 110 nm, top contact type) was prepared using the compound (3), and the charge mobility was measured. Results suggesting semiconductor performance of 3 × 10 −3 cm 2 / Vs were obtained.
本発明により、電子ペーパーや情報タグ等に適用できる、有機半導体材料として有用なペンタフルオロスルファニル基を有する複素環オリゴマー化合物を提供することができる。 According to the present invention, a heterocyclic oligomer compound having a pentafluorosulfanyl group useful as an organic semiconductor material that can be applied to electronic paper, information tags, and the like can be provided.
Claims (4)
で示されるペンタフルオロスルファニル基を有するチオフェンオリゴマー化合物である請求項１記載のペンタフルオロスルファニル基を有する複素環オリゴマー化合物。 A heterocyclic oligomer compound having a pentafluorosulfanyl group is represented by the general formula (1)
The heterocyclic oligomer compound having a pentafluorosulfanyl group according to claim 1, which is a thiophene oligomer compound having a pentafluorosulfanyl group represented by formula (1).
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| WO2015041026A1 (en) | 2013-09-20 | 2015-03-26 | 宇部興産株式会社 | Benzobis (thiadiazole) derivative, ink containing same, and organic electronic device using same |
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| CN105793269A (en) * | 2013-09-20 | 2016-07-20 | 宇部兴产株式会社 | Benzobis(thiadiazole) derivative, ink containing same, and organic electronic device using same |
| US9978954B2 (en) | 2013-09-20 | 2018-05-22 | Ube Industries, Ltd. | Benzobis (thiadiazole) derivative, ink comprising same, and organic electronic device comprising same |
| KR102218514B1 (en) | 2013-09-20 | 2021-02-19 | 가부시키가이샤 퓨쳐 잉크 | Benzobis (thiadiazole) derivative, ink containing same, and organic electronic device using same |
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