JP4387781B2 - Carborane compounds and conductive materials - Google Patents
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本発明は、新規な有機化合物に関する。 The present invention relates to a novel organic compound.
カルボラン化合物は特許文献１などに記載されるように、ＭＲＩ関連医薬品として、および癌の放射線治療における中性子捕捉剤として利用される化合物である。 The carborane compound is a compound that is used as an MRI-related drug and as a neutron capture agent in cancer radiotherapy as described in Patent Document 1 and the like.
これまでにカルボラン化合物を導電材料として利用することは着目されていなかった。 So far, the use of carborane compounds as conductive materials has not been noticed.
本発明者らはカルボラン化合物が導電材料として利用できる可能性を模索した。そこで２つの炭素原子と１０個のボラン原子との球状骨格で形成されるカルボラン骨格のみのカルボラン化合物などの導電特性を調べようとしたが導電特性を求めることができなかった。というのも、そのような化合物は膜化することができず、電極で挟んで測定することができなかったからである。 The present inventors sought the possibility that a carborane compound can be used as a conductive material. Therefore, an attempt was made to investigate the conductive characteristics of a carborane compound having only a carborane skeleton formed of a spherical skeleton of two carbon atoms and 10 borane atoms, but the conductive characteristics could not be obtained. This is because such a compound could not be formed into a film and could not be measured by being sandwiched between electrodes.
よって本発明では、導電特性を有する新規カルボラン化合物を提供することを目的とする。 Therefore, an object of the present invention is to provide a novel carborane compound having conductive properties.
すなわち、本発明のカルボラン化合物は、下記一般式［１］〜［３］で示されることを
特徴とする。尚、下記一般式［１］〜［３］のうち、下記に示される化合物が本発明に該当する。
（式中、Ｒ１〜Ｒ４は、水素原子、置換あるいは無置換のアルキル基、置換あるいは無置換のアリール基、置換あるいは無置換の複素環基、置換あるいは無置換の縮合多環芳香族基または置換あるいは無置換の縮合多環複素環基を表わし、Ｌが１の場合、少なくとも１つは、置換あるいは無置換の縮合多環芳香族基または置換あるいは無置換の縮合多環複素環基を表わす。Ｒ１〜Ｒ４は、同じであっても異なっていてもよい。 (Wherein R1 to R4 are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group or a substituted group; Alternatively, it represents an unsubstituted condensed polycyclic heterocyclic group, and when L is 1, at least one represents a substituted or unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted condensed polycyclic heterocyclic group. R1 to R4 may be the same or different.
Ｌは、１乃至２０の整数を表す。） L represents an integer of 1 to 20. )
（式中、Ｒ５〜Ｒ７は、水素原子、置換あるいは無置換のアルキル基、置換あるいは無置換のアリール基、置換あるいは無置換の複素環基、置換あるいは無置換の縮合多環芳香族基または置換あるいは無置換の縮合多環複素環基を表わし、少なくとも１つは、置換あるいは無置換の縮合多環芳香族基または置換あるいは無置換の縮合多環複素環基を表わす。Ｒ５〜Ｒ７は、同じであっても異なっていてもよい。 Wherein R5 to R7 are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group or a substituted group Alternatively, it represents an unsubstituted condensed polycyclic heterocyclic group, and at least one represents a substituted or unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted condensed polycyclic heterocyclic group, and R5 to R7 are the same. Or different.
Ａｒ１は、置換あるいは無置換のアリーレン基、２価の、置換あるいは無置換の複素環基、置換あるいは無置換の縮合多環芳香族環基または置換あるいは無置換の縮合多環複素環基を表わす。） Ar1 represents a substituted or unsubstituted arylene group, a divalent substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic ring group, or a substituted or unsubstituted condensed polycyclic heterocyclic group. . )
（式中、Ｒ８〜Ｒ１０は、水素原子、置換あるいは無置換のアルキル基、置換あるいは無置換のアリール基、置換あるいは無置換の複素環基、置換あるいは無置換の縮合多環芳香族基または置換あるいは無置換の縮合多環複素環基を表わし、少なくとも１つは、置換あるいは無置換の縮合多環芳香族基または置換あるいは無置換の縮合多環複素環基を表わす。Ｒ８〜Ｒ１０は、同じであっても異なっていてもよい。 Wherein R8 to R10 are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group or a substituted group Alternatively, it represents an unsubstituted fused polycyclic heterocyclic group, and at least one represents a substituted or unsubstituted fused polycyclic aromatic group or a substituted or unsubstituted fused polycyclic heterocyclic group, and R8 to R10 are the same. Or different.
Ａｒ２は、３価の、置換あるいは無置換の芳香環基、置換あるいは無置換の複素環基、置換あるいは無置換の縮合多環芳香族環基または置換あるいは無置換の縮合多環複素環基を表わす。） Ar2 represents a trivalent, substituted or unsubstituted aromatic ring group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic ring group, or a substituted or unsubstituted condensed polycyclic heterocyclic group. Represent. )
本発明により、縮合多環芳香族置換基あるいは縮合多環複素環置換基を有する化合物であって、導電特性を有する新規カルボラン化合物を提供することができた。また剥がれたり亀裂が入らない良好に膜化できる化合物を提供することができた。 According to the present invention, it is possible to provide a novel carborane compound having a conductive property, which is a compound having a condensed polycyclic aromatic substituent or a condensed polycyclic heterocyclic substituent. Moreover, the compound which can be favorably formed into a film without peeling or cracking was able to be provided.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のカルボラン化合物は、２個の炭素原子と１０個のボラン原子からなる球状化合物を基本骨格として有する。例えば、一般式［１］で示されるカルボラン化合物のＬ＝１は、Ｃ2Ｈ10Ｂ10Ｒ１Ｒ２Ｒ３Ｒ４の分子式で表せる。 The carborane compound of the present invention has a spherical compound composed of 2 carbon atoms and 10 borane atoms as a basic skeleton. For example, L = 1 of the carborane compound represented by the general formula [1] can be represented by a molecular formula of C 2 H 10 B 10 R1R2R3R4.
上記一般式［１］〜［３］における置換基の具体例を以下に示す。 Specific examples of the substituents in the general formulas [1] to [3] are shown below.
アルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｔｅｒ−ブチル基、オクチル基などが挙げられる。 Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a ter-butyl group, and an octyl group.
アリール基としては、フェニル基、ビフェニル基、ターフェニル基などが挙げられる。
複素環基としては、チエニル基、ピロリル基、ピリジル基、ビピリジル基、ターピリジル基、オキサゾリル基、オキサジアゾリル基、チアゾリル基、チアジアゾリル基、ターチエニル基などが挙げられる。
Examples of the aryl group include a phenyl group, a biphenyl group, and a terphenyl group.
Examples of the heterocyclic group include thienyl group, pyrrolyl group, pyridyl group, bipyridyl group, terpyridyl group, oxazolyl group, oxadiazolyl group, thiazolyl group, thiadiazolyl group, and tertenyl group.
縮合多環芳香族基としては、フルオレニル基、ナフチル基、フルオランテニル基、アンスリル基、フェナンスリル基、ピレニル基、テトラセニル基、ペンタセニル基、トリフェニレニル基、ペリレニル基などが挙げられる。 Examples of the condensed polycyclic aromatic group include a fluorenyl group, a naphthyl group, a fluoranthenyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a tetracenyl group, a pentacenyl group, a triphenylenyl group, and a perylenyl group.
縮合多環複素環基としては、カルバゾリル基、フェナントロリル基、ジアザフルオレニル基、アクリジニル基などが挙げられる。 Examples of the condensed polycyclic heterocyclic group include a carbazolyl group, a phenanthroyl group, a diazafluorenyl group, and an acridinyl group.
アリーレン基としては、フェニレン基、ビフェニレン基、ターフェニレン基、ビピリジレン基、ターピリジレン基、フルオレニレン基、フェナントロレニレン基などが挙げられる。 Examples of the arylene group include a phenylene group, a biphenylene group, a terphenylene group, a bipyridylene group, a terpyridylene group, a fluorenylene group, and a phenanthrolenylene group.
上記置換基が有してもよい置換基としては、メチル基、エチル基、プロピル基などのアルキル基、フェニル基、ビフェニル基などのアリール基、チエニル基、ピロリル基、ピリジル基などの複素環基、フルオレニル基、ナフチル基、フルオランテニル基、アンスリル基、フェナンスリル基、ピレニル基、テトラセニル基、ペンタセニル基、トリフェニレニル基、ペリレニル基などの縮合多環芳香族基、カルバゾリル基、フェナントロリル基、ジアザフルオレニル基、アクリジニル基などの縮合多環複素環基、ジメチルアミノ基、ジエチルアミノ基、ジベンジルアミノ基、ジフェニルアミノ基、ジトリルアミノ基、ジアニソリルアミノ基などのアミノ基、メトキシル基、エトキシル基、プロポキシル基、フェノキシル基などのアルコキシル基、シアノ基、フッ素、塩素、臭素、ヨウ素などのハロゲン原子などが挙げられる。 Examples of the substituent that the substituent may have include an alkyl group such as a methyl group, an ethyl group, and a propyl group, an aryl group such as a phenyl group and a biphenyl group, a heterocyclic group such as a thienyl group, a pyrrolyl group, and a pyridyl group. , Fluorenyl group, naphthyl group, fluoranthenyl group, anthryl group, phenanthryl group, pyrenyl group, tetracenyl group, pentacenyl group, triphenylenyl group, perylenyl group and other condensed polycyclic aromatic groups, carbazolyl group, phenanthryl group, diazafur Condensed polycyclic heterocyclic groups such as oleenyl group and acridinyl group, dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group, ditolylamino group, amino group such as dianisolylamino group, methoxyl group, ethoxyl group, Alkoxyl groups such as propoxyl group and phenoxyl group, Anomoto, fluorine, chlorine, bromine, a halogen atom such as iodine.
次に、本発明のカルボラン化合物の代表例を以下に挙げるが、本発明はこれらに限定されるものではない。 Next, typical examples of the carborane compound of the present invention are listed below, but the present invention is not limited thereto.
一般式（１）で示されるカルボラン化合物 Carborane compound represented by general formula (1)
一般式（２）で示されるカルボラン化合物 Carborane compound represented by general formula (2)
一般式（３）で示されるカルボラン化合物 Carborane compound represented by general formula (3)
本発明のカルボラン化合物は、一般的に知られている方法で合成でき、例えば、
Ｒ．Ｋｏｓｔｅｒ，Ｈｏｕｂｅｎ−Ｗｅｙｌ Ｍｅｔｈｏｄｅｎ ｄｅｒ Ｏｒｇａｎｉｓｃｈｅｎ Ｃｈｅｍｉｅ，Ｏｒｇａｎｏｂｏｒ Ｖｅｒｂｉｎｄｕｎｇｅｎ ＩＩＩ，Ｂａｎｄ ＸＩＩＩ／３ｃ，Ｇｅｏｇ Ｔｈｉｅｍｅ Ｖｅｒｌａｇ，Ｓｔｕｔｔｇａｒｔ，１９８４．
Ｒ．Ｎ．Ｇｒｉｍｅｓ，Ｃａｒｂｏｒａｎｅｓ，Ａｃａｄｅｍｉｃ Ｐｒｅｓｓ，Ｎｅｗ Ｙｏｒｋ，１９７０．
Ｗ．Ｓｉｅｂｅｒｔ，Ａｄｖａｎｃｅｓ ｉｎ Ｂｏｒｏｎ Ｃｈｅｍｉｓｔｒｙ，１９９７．
Ｍａｒｋ Ａ．Ｆｏｘ，Ｊｏｕｒｎａｌ ｏｆ Ｍａｔｅｒｉａｌｓ Ｃｈｅｍｉｓｔｒｙ，２００２，１２，１３０１−１３０６．
などに記載の方法でカルボラン化合物中間体を得ることができる。
The carborane compound of the present invention can be synthesized by a generally known method, for example,
R. Koster, Houben-Weyl Method der Organischen Chemie, Organobor Verbundungen III, Band XIII / 3c, Geog Thieme Verlag, Stuttgart, 1984.
R. N. Grimes, Carbonares, Academic Press, New York, 1970.
W. Siebert, Advances in Boron Chemistry, 1997.
Mark A. Fox, Journal of Materials Chemistry, 2002, 12, 1301-1306.
A carborane compound intermediate can be obtained by the method described in the above.
さらにパラジウム触媒を用いたＳｕｚｕｋｉ Ｃｏｕｐｌｉｎｇ法（例えばＣｈｅｍ．Ｒｅｖ．１９９５，９５，２４５７．）、ニッケル触媒を用いたＹａｍａｍｏｔｏ法（例えばＢｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊｐｎ．，５１，２０９１，１９７８．）などの合成法でカルボラン化合物を得ることができる。 Further, Suzuki Coupling method using a palladium catalyst (for example, Chem. Rev. 1995, 95, 2457.), Yamamoto method using a nickel catalyst (for example, Bull. Chem. Soc. Jpn., 51, 2091, 1978.), etc. A carborane compound can be obtained by a synthesis method.
尚、本発明の化合物に類似する一般式（４）〜（９）で示されるカルボラン化合物も導電特性があるものと思われる。 The carborane compounds represented by the general formulas (4) to (9) similar to the compounds of the present invention are also considered to have conductive properties.
（式中、Ｒ１１〜Ｒ１２は、水素原子、置換あるいは無置換のアルキル基、置換あるいは無置換のアリール基、置換あるいは無置換の複素環基、置換あるいは無置換の縮合多環芳香族基または置換あるいは無置換の縮合多環複素環基を表わし、ｍ＝１の場合、少なくとも１つは、置換あるいは無置換の縮合多環芳香族基または置換あるいは無置換の縮合多環複素環基を表わす。Ｒ１１〜Ｒ１２は、同じであっても異なっていてもよい。 Wherein R11 to R12 are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group or a substituted group Alternatively, it represents an unsubstituted condensed polycyclic heterocyclic group, and when m = 1, at least one represents a substituted or unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted condensed polycyclic heterocyclic group. R11 to R12 may be the same or different.
ｍは、１乃至２０の整数を表す。） m represents an integer of 1 to 20. )
以下に具体例を示す。 Specific examples are shown below.
（式中、Ｒ１３〜Ｒ１４は、水素原子、置換あるいは無置換のアルキル基、置換あるいは無置換のアリール基、置換あるいは無置換の複素環基、置換あるいは無置換の縮合多環芳香族基または置換あるいは無置換の縮合多環複素環基を表わし、ｎ＝１の場合、少なくとも１つは、置換あるいは無置換の縮合多環芳香族基または置換あるいは無置換の縮合多環複素環基を表わす。Ｒ１３〜Ｒ１４は、同じであっても異なっていてもよい。 Wherein R13 to R14 are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group or a substituted group Alternatively, it represents an unsubstituted condensed polycyclic heterocyclic group, and when n = 1, at least one represents a substituted or unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted condensed polycyclic heterocyclic group. R13 to R14 may be the same or different.
ｎは、１乃至２０の整数を表す。） n represents an integer of 1 to 20. )
以下に具体例を示す。 Specific examples are shown below.
（式中、Ｒ１５は、置換あるいは無置換の縮合多環芳香族基または置換あるいは無置換の縮合多環複素環基を表わす。 (In the formula, R15 represents a substituted or unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted condensed polycyclic heterocyclic group.
Ａｒ３は、置換あるいは無置換のアリーレン基、２価の、置換あるいは無置換の複素環基、置換あるいは無置換の縮合多環芳香族環基または置換あるいは無置換の縮合多環複素環基を表わす。） Ar3 represents a substituted or unsubstituted arylene group, a divalent substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic ring group, or a substituted or unsubstituted condensed polycyclic heterocyclic group. . )
以下に具体例を示す。 Specific examples are shown below.
（式中、Ｒ１６は、置換あるいは無置換の縮合多環芳香族基または置換あるいは無置換の縮合多環複素環基を表わす。 (Wherein R16 represents a substituted or unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted condensed polycyclic heterocyclic group.
Ａｒ４は、置換あるいは無置換のアリーレン基、２価の、置換あるいは無置換の複素環基、置換あるいは無置換の縮合多環芳香族環基または置換あるいは無置換の縮合多環複素環基を表わす。） Ar4 represents a substituted or unsubstituted arylene group, a divalent substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic ring group, or a substituted or unsubstituted condensed polycyclic heterocyclic group. . )
以下に具体例を示す。 Specific examples are shown below.
（式中、Ｒ１７は、置換あるいは無置換の縮合多環芳香族基または置換あるいは無置換の縮合多環複素環基を表わす。 (In the formula, R17 represents a substituted or unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted condensed polycyclic heterocyclic group.
Ａｒ５は、３価の、置換あるいは無置換の芳香環基、置換あるいは無置換の複素環基、置換あるいは無置換の縮合多環芳香族環基または置換あるいは無置換の縮合多環複素環基を表わす。） Ar5 represents a trivalent substituted or unsubstituted aromatic ring group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic ring group, or a substituted or unsubstituted condensed polycyclic heterocyclic group. Represent. )
以下に具体例を示す。 Specific examples are shown below.
（式中、Ｒ１８は、置換あるいは無置換の縮合多環芳香族基または置換あるいは無置換の縮合多環複素環基を表わす。 (In the formula, R18 represents a substituted or unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted condensed polycyclic heterocyclic group.
Ａｒ６は、３価の、置換あるいは無置換の芳香環基、置換あるいは無置換の複素環基、置換あるいは無置換の縮合多環芳香族環基または置換あるいは無置換の縮合多環複素環基を表わす。） Ar6 is a trivalent substituted or unsubstituted aromatic ring group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic ring group, or a substituted or unsubstituted condensed polycyclic heterocyclic group. Represent. )
以下に具体例を示す。 Specific examples are shown below.
＜実施例１（例示化合物Ｎｏ．５の合成）＞ <Example 1 (Synthesis of Exemplified Compound No. 5)>
３００ｍｌ三ツ口フラスコに、カルボラン化合物［１］５．０ｇ（１６．９ｍｍｏｌ）および酢酸１００ｍｌを入れ、次いで濃硝酸５ｍｌ、濃硫酸５ｍｌ、ヨウ素９．４ｇ（３７．１ｍｍｏｌ）を入れ、７０℃で６時間攪拌した後、反応液を氷水に注加し有機層をクロロホルムで抽出し無水硫酸ナトリウムで乾燥後、シリカゲルカラム（ヘキサン＋トルエン展開溶媒）で精製し、ジヨード体［２］を６．７ｇ（収率７２％）得た。 A 300 ml three-necked flask is charged with 5.0 g (16.9 mmol) of carborane compound [1] and 100 ml of acetic acid, followed by 5 ml of concentrated nitric acid, 5 ml of concentrated sulfuric acid, and 9.4 g (37.1 mmol) of iodine at 70 ° C. for 6 hours. After stirring, the reaction solution was poured into ice water, the organic layer was extracted with chloroform, dried over anhydrous sodium sulfate, and purified with a silica gel column (hexane + toluene developing solvent) to obtain 6.7 g (yield) of diiodide [2]. (Rate 72%).
次に、３００ｍｌ三ツ口フラスコに、上記ジヨード体［２］３．０ｇ（５．４７ｍｍｏｌ）、パラジウム触媒０．１９ｇ（０．２７ｍｍｏｌ）およびジエチルエーテル８０ｍｌを入れ、窒素雰囲気中０℃で攪拌下、別途調製した２−ヨード−９，９−ジメチルフルオレン５．３ｇ（１６．４ｍｍｏｌ）、マグネシウム０．４８ｇ（１９．７ｍｍｏｌ）およびジエチルエーテルのグリニヤール試薬を滴下した。室温で１２時間攪拌した後、水を加え有機層をクロロホルムで抽出し無水硫酸ナトリウムで乾燥後、シリカゲルカラム（ヘキサン＋トルエン展開溶媒）で精製し、例示化合物Ｎｏ．５を２．４ｇ（収率６５％）得た。質量スペクトルはｍ／ｚ＝６８３であった。 Next, 3.0 g (5.47 mmol) of the above diiodide [2], 0.19 g (0.27 mmol) of palladium catalyst and 80 ml of diethyl ether were placed in a 300 ml three-necked flask, and the mixture was separately stirred at 0 ° C. in a nitrogen atmosphere. The prepared 2-iodo-9,9-dimethylfluorene (5.3 g, 16.4 mmol), magnesium (0.48 g, 19.7 mmol) and diethyl ether Grignard reagent were added dropwise. After stirring at room temperature for 12 hours, water was added, the organic layer was extracted with chloroform, dried over anhydrous sodium sulfate, and purified with a silica gel column (hexane + toluene developing solvent). 2.4 g (yield 65%) of 5 was obtained. The mass spectrum was m / z = 683.
化合物Ｎｏ．５の導電測定を試みた。陽極としてのＩＴＯ上に蒸着で化合物Ｎｏ．５を成膜した。成膜条件は蒸着温度３００℃（加熱ボード温度）、チャンバー内圧力１０-4Ｐａ、膜厚は１μｍであった。化合物Ｎｏ．５の成膜後にそのまま引き続いて（真空を破らずに）、化合物Ｎｏ．５の膜上に陰極となるＡｌを成膜した。得られた素子の電極間に定電圧１０Ｖを印加して導電率を求めたところ、およそ導電率は１．１ｘ１０5ｃｍ／Ωであり導電性の存在を観察した。 Compound No. 5 electrical conductivity measurements were attempted. Compound No. 1 was deposited on ITO as the anode by vapor deposition. 5 was deposited. The film formation conditions were an evaporation temperature of 300 ° C. (heating board temperature), a chamber internal pressure of 10 −4 Pa, and a film thickness of 1 μm. Compound No. 5 after film formation (without breaking the vacuum). On the film No. 5, Al serving as a cathode was formed. When a constant voltage of 10 V was applied between the electrodes of the obtained device to determine the conductivity, the conductivity was approximately 1.1 × 10 5 cm / Ω, and the presence of conductivity was observed.
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