JP6026824B2 - Method for producing radical anion of aromatic nitro compound - Google Patents
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Description
本発明は、芳香族ニトロ化合物のラジカルアニオンを、試薬の加熱によって製造する方法に関する。 The present invention relates to a method for producing a radical anion of an aromatic nitro compound by heating a reagent.
フリーラジカルは、一般的に反応性が高く不安定なものが多いが、ニトロベンゼンなどの芳香族ニトロ化合物のラジカルアニオンは、有機溶媒中で比較的に安定するものとして知られており、各種の有機合成反応に応用することができる。たとえば、ニトロベンゼンラジカルアニオンは、アニリンの合成に応用することができる。 Free radicals are generally highly reactive and unstable, but radical anions of aromatic nitro compounds such as nitrobenzene are known to be relatively stable in organic solvents, and various organic It can be applied to synthesis reactions. For example, the nitrobenzene radical anion can be applied to the synthesis of aniline.
このような芳香族ニトロ化合物のラジカルアニオンは、非特許文献１に記載のように、テトラ−ｎ−ブチル−アンモニウム−パークロレートが添加されたジメトキシエタン溶媒中で、芳香族ニトロ化合物に電圧を印加して、電気分解的に製造することができる。また、ナトリウムなどのアルカリ金属の単体を用いて芳香族ニトロ化合物を還元することによっても、芳香族ニトロ化合物のラジカルアニオンの製造は可能である。なお、非特許文献２には、水酸化物イオンを、有機溶媒中で還元剤として利用可能であることが記載されているが、水酸化物イオンによって芳香族ニトロ化合物を還元し、芳香族ニトロ化合物のラジカルアニオンを製造する方法は、未だ実現されていない。 As described in Non-Patent Document 1, such a radical anion of an aromatic nitro compound applies a voltage to the aromatic nitro compound in a dimethoxyethane solvent to which tetra-n-butyl-ammonium-perchlorate is added. Thus, it can be produced electrolytically. Moreover, the radical anion of an aromatic nitro compound can also be produced by reducing the aromatic nitro compound using a simple substance of an alkali metal such as sodium. Non-Patent Document 2 describes that hydroxide ions can be used as a reducing agent in an organic solvent. However, aromatic nitro compounds are reduced with hydroxide ions, and aromatic nitro compounds are reduced. A method for producing a radical anion of a compound has not been realized yet.
芳香族ニトロ化合物のラジカルアニオンは、電子供与体として働くので、化学電池への応用が期待されている。しかしながら、上述したような従来の製造方法では、製造のための装置が複雑となり、また、製造に必要なエネルギーが大きくなるので、芳香族ニトロ化合物のラジカルアニオンを用いた化学電池の実現が難しい。 Since the radical anion of an aromatic nitro compound acts as an electron donor, it is expected to be applied to a chemical battery. However, in the conventional manufacturing method as described above, an apparatus for manufacturing becomes complicated and energy required for manufacturing becomes large, so that it is difficult to realize a chemical battery using a radical anion of an aromatic nitro compound.
本発明は、上述した課題を解決するためのものであり、簡単に行うことができる芳香族ニトロ化合物のラジカルアニオンの製造方法を提供することを目的とする。 The present invention is intended to solve the above-described problems, and an object thereof is to provide a method for producing a radical anion of an aromatic nitro compound that can be easily performed.
本発明は、ニトロベンゼンまたはニトロナフタレンのいずれかと水酸化テトラアルキルアンモニウムとを、ニトロベンゼン（ただし、前記芳香族ニトロ化合物がニトロベンゼンであるときを除く）、アセトン、アセトニトリル、テトラヒドロフラン、またはジメチルスルホキシドのうちのいずれか１つであるか、または、いずれか２つ以上を混合した有機溶媒であって、アルコールおよび水を含まない有機溶媒中で６０℃以上に加熱することを特徴とするニトロベンゼンまたはニトロナフタレンのラジカルアニオンの製造方法である。
The present invention relates to any one of nitrobenzene or nitronaphthalene and tetraalkylammonium hydroxide selected from nitrobenzene (except when the aromatic nitro compound is nitrobenzene), acetone, acetonitrile, tetrahydrofuran, or dimethyl sulfoxide. A nitrobenzene or nitronaphthalene , which is an organic solvent in which any one or two or more of them are mixed and heated to 60 ° C. or higher in an organic solvent not containing alcohol and water It is a manufacturing method of a radical anion.
また本発明は、ニトロベンゼンまたはニトロナフタレンのいずれかの芳香族ニトロ化合物がニトロベンゼン（ただし、前記芳香族ニトロ化合物がニトロベンゼンであるときを除く）、アセトン、アセトニトリル、テトラヒドロフラン、またはジメチルスルホキシドのうちのいずれか１つであるか、または、いずれか２つ以上を混合した有機溶媒に溶解された第１の溶液と、水酸化テトラアルキルアンモニウムが前記有機溶媒に溶解された第２の溶液と、を準備する第１の工程と、
前記第１の溶液と前記第２の溶液とを混合し、６０℃以上に加熱する第２の工程と、を含み、
前記第１の工程では、前記第１の溶液中または前記第２の溶液中にアルコールまたは水が含まれているとき、該アルコールまたは水を除去することを特徴とするニトロベンゼンまたはニトロナフタレンのラジカルアニオンの製造方法である。
Further, in the present invention, the aromatic nitro compound of either nitrobenzene or nitronaphthalene is any one of nitrobenzene (except when the aromatic nitro compound is nitrobenzene), acetone, acetonitrile, tetrahydrofuran, or dimethyl sulfoxide. one is either, or, to prepare a first solution in an organic solvent obtained by mixing any two or more, a second solution tetraalkylammonium hydroxide is dissolved in the organic solvent, the A first step;
Mixing the first solution and the second solution and heating to 60 ° C. or higher,
In the first step, when alcohol or water is contained in the first solution or the second solution, the alcohol or water is removed, and the radical anion of nitrobenzene or nitronaphthalene It is a manufacturing method.
本発明によれば、有機溶媒中で安定なニトロベンゼンまたはニトロナフタレン（以下、芳香族ニトロ化合物ということがある）のラジカルアニオンを、試薬の加熱という簡単な方法によって製造することができる。したがって、熱エネルギーを直接電気化学エネルギーに変換および蓄積させるとともに、その電気化学エネルギーを直接電気エネルギーとして取り出せる、全く新しいタイプの化学電池の構成が可能になるものと期待される。
According to the present invention, a radical anion of nitrobenzene or nitronaphthalene (hereinafter sometimes referred to as an aromatic nitro compound ) that is stable in an organic solvent can be produced by a simple method of heating a reagent. Therefore, it is expected that a completely new type of chemical battery that can convert and store thermal energy directly into electrochemical energy and extract the electrochemical energy directly as electrical energy will be possible.
以下に、芳香族ニトロ化合物のラジカルアニオンを、簡単に製造することができる新規の製造方法について説明する。この新規の製造方法は、たとえば芳香族ニトロ化合物の１つであるニトロベンゼンと従来公知の水酸化物イオンとを、従来公知の有機溶媒中で６０℃以上に加熱することを特徴とする。この新規の製造方法の一態様としては、有機溶媒に水酸化物イオンを溶解させた溶液Ａを調製する工程と、有機溶媒にニトロベンゼンを溶解させた溶液Ｂを調製する工程と、溶液Ａと溶液Ｂとを混合して溶液Ｃとし、加熱する工程とを含む製造工程が挙げられる。以下に、この製造工程について説明する。 Below, the novel manufacturing method which can manufacture the radical anion of an aromatic nitro compound easily is demonstrated. This novel production method is characterized in that, for example, nitrobenzene, which is one of aromatic nitro compounds, and a conventionally known hydroxide ion are heated to 60 ° C. or higher in a conventionally known organic solvent. As one aspect of this novel manufacturing method, a step of preparing a solution A in which hydroxide ions are dissolved in an organic solvent, a step of preparing a solution B in which nitrobenzene is dissolved in an organic solvent, a solution A and a solution The manufacturing process including the process of mixing B with the solution C and heating is mentioned. Below, this manufacturing process is demonstrated.
＜溶液Ａの調製工程＞
水酸化物イオンを溶解するための有機溶媒として、１ｍｌのジメチルスルホキシド（ＤＭＳＯ、和光純薬製）を用意した。そして、この有機溶媒に対して、濃度が２５ｗｔ％である、水酸化テトラメチルアンモニウム（ＴＭＡＨ）のメタノール溶液(無色透明の液体、ＡＬＦ社製)を４２２μｌ加え、８０℃に加熱して、メタノールを除去した。これによって、水酸化物イオンを有する化合物（水酸化化合物）であるＴＭＡＨが１Ｍ（モーラー；mol／ｌ）の濃度で溶解したＤＭＳＯ溶液（溶液Ａ）が調製された。
<Preparation process of solution A>
As an organic solvent for dissolving hydroxide ions, 1 ml of dimethyl sulfoxide (DMSO, manufactured by Wako Pure Chemical Industries) was prepared. Then, 422 μl of a tetramethylammonium hydroxide (TMAH) methanol solution (colorless and transparent liquid, manufactured by ALF) having a concentration of 25 wt% is added to this organic solvent, heated to 80 ° C., and methanol is added. Removed. As a result, a DMSO solution (solution A) in which TMAH, which is a compound having hydroxide ions (a hydroxide compound), was dissolved at a concentration of 1 M (molar; mol / l) was prepared.
＜溶液Ｂの調製工程＞
ニトロベンゼンを溶解するための有機溶媒として、１ｍｌのＤＭＳＯ（和光純薬製）を用意した。そして、この有機溶媒に対して、ニトロベンゼン（和光純薬製）を、１０３μｌ加えた。これによって、ニトロベンゼンが１Ｍ（モーラー；mol／ｌ）の濃度で溶解したＤＭＳＯ溶液（溶液Ｂ）が調製された。
<Preparation process of solution B>
As an organic solvent for dissolving nitrobenzene, 1 ml of DMSO (manufactured by Wako Pure Chemical Industries) was prepared. And 103 microliters of nitrobenzene (made by Wako Purechemical) was added with respect to this organic solvent. Thereby, a DMSO solution (solution B) in which nitrobenzene was dissolved at a concentration of 1 M (molar; mol / l) was prepared.
＜溶液Ｃの調製および加熱工程＞
溶液Ａと溶液Ｂとを１対１の割合（体積割合）で混合して、ニトロベンゼンおよびＴＭＡＨが溶解したＤＭＳＯ溶液（溶液Ｃ）を調製した。その後、溶液Ｃを８０℃に加熱した。
<Preparation and heating step of solution C>
Solution A and solution B were mixed at a ratio of 1 to 1 (volume ratio) to prepare a DMSO solution (solution C) in which nitrobenzene and TMAH were dissolved. Thereafter, Solution C was heated to 80 ° C.
溶液Ｃの加熱によってニトロベンゼンラジカルアニオンが製造されているかを確認するために、ＥＳＲ（電子スピン共鳴）によるスペクトルの測定を行った。具体的には、溶液Ｃの加熱前に、アルゴンガスを通気することで、ＥＳＲスペクトルに影響を与える酸素を除去した後、ＥＳＲ測定用セルに溶液Ｃを封入し、セルごと８０℃に加熱しながらＥＳＲスペクトルの測定を行った。 In order to confirm whether the nitrobenzene radical anion was produced by heating the solution C, the spectrum was measured by ESR (electron spin resonance). Specifically, before the solution C is heated, argon gas is vented to remove oxygen that affects the ESR spectrum, and then the solution C is sealed in an ESR measurement cell, and the cell is heated to 80 ° C. The ESR spectrum was measured.
このようにして測定されたＥＳＲスペクトルを、図１に示す。また、比較のために、公知資料（新実験化学講座 13.有機構造［II］p.935 丸善（1979））に基づいたニトロベンゼンラジカルアニオンのＥＳＲスペクトルを、図２に示す。図１に示すグラフは、セルに対して磁場を印加しながら、ｇ値が２．００３となる周波数の電磁波を入射したときの、セルによる電磁波の吸収強度を示している。図１および図２において、横軸は磁場の大きさ［ｍＴ］を表し、縦軸は電磁波の吸収強度を表している。 The ESR spectrum thus measured is shown in FIG. For comparison, FIG. 2 shows an ESR spectrum of a nitrobenzene radical anion based on a known document (New Experimental Chemistry Course 13. Organic Structure [II] p.935 Maruzen (1979)). The graph shown in FIG. 1 shows the absorption intensity of an electromagnetic wave by a cell when an electromagnetic wave having a frequency with a g value of 2.003 is incident while a magnetic field is applied to the cell. 1 and 2, the horizontal axis represents the magnitude of the magnetic field [mT], and the vertical axis represents the electromagnetic wave absorption intensity.
図１のグラフから、スペクトルの線幅ΔＨｐ‐ｐ（ピークとピークとの間隔を磁場の大きさで表した値）が、０．０４２ｍＴと算出された。また、パラ位の水素原子と不対電子との間の超微細結合定数ＡＨｐａｒａが０．３９０ｍＴと算出され、オルト位の水素原子と不対電子との間の超微細結合定数ＡＨｏｒｔｈｏが０．３３９ｍＴと算出され、メタ位の水素原子と不対電子との間の超微細結合定数ＡＨｍｅｔａが０．１０１ｍＴと算出され、窒素原子と不対電子との間の超微細結合定数ＡＮが１．０４ｍＴと算出された。これに対して、上記公知資料によれば、超微細結合定数ＡＨｐａｒａが０．３８２ｍＴであり、超微細結合定数ＡＨｏｒｔｈｏが０．３３０ｍＴであり、超微細結合定数ＡＨｍｅｔａが０．１０３ｍＴであり、超微細結合定数ＡＮが１．０６２ｍＴであることから、各超微細結合定数はそれぞれ近似した値であり、溶液Ｃを８０℃に加熱することで、ニトロベンゼンラジカルアニオンが製造されることが確認された。 From the graph of FIG. 1, the spectral line width ΔH pp (a value obtained by expressing the interval between peaks by the magnitude of the magnetic field) was calculated to be 0.042 mT. The ultrafine coupling constant A Hpara between the para-position of the hydrogen atoms and the unpaired electrons is calculated as 0.390MT, hyperfine coupling constants A Hortho between ortho hydrogen atoms and unpaired electrons 0 Calculated as .339 mT, the hyperfine coupling constant A Hmeta between the hydrogen atom at the meta position and the unpaired electron is calculated as 0.101 mT, and the hyperfine coupling constant A N between the nitrogen atom and the unpaired electron is It was calculated to be 1.04 mT. On the other hand, according to the above-mentioned known documents, the hyperfine coupling constant A Hpara is 0.382 mT, the hyperfine coupling constant A Horse is 0.330 mT, and the hyperfine coupling constant A Hmeta is 0.103 mT. since hyperfine coupling constant a N is 1.062MT, the hyperfine coupling constant is a value approximating each by heating the solution C to 80 ° C., confirmed that the nitrobenzene radical anion is produced It was done.
次に、溶液Ｃの加熱工程において、加熱温度を、５０℃、６０℃、６５℃、７０℃、および８０℃にそれぞれ設定して、加熱時間とＥＳＲにおける吸収強度との関係を調べた。図３に、加熱時間と吸収強度との関係を示す。図３において、横軸は加熱時間［ｓ（秒）］を表し、縦軸は吸収強度ａＴを表している。ここで、吸収強度ａＴは、ＥＳＲスペクトルにおける複数のピークにおける吸収強度の算術平均値であってもよいし、いずれか１つのピークにおける吸収強度であってもよい。また、図３における白の丸点は加熱温度が５０℃のときの測定値を示し、白の四角点は加熱温度が６０°のときの測定値を示し、白の三角点は加熱温度が６５°のときの測定値を示し、黒の丸点は加熱温度が７０℃のときの測定値を示し、黒の四角点は加熱温度が８０°のときの測定値を示す。 Next, in the heating step of the solution C, the heating temperature was set to 50 ° C., 60 ° C., 65 ° C., 70 ° C., and 80 ° C., respectively, and the relationship between the heating time and the absorption intensity in ESR was examined. FIG. 3 shows the relationship between the heating time and the absorption intensity. 3, the horizontal axis heating time represents [s (seconds) and the vertical axis represents absorption intensity a T. Here, the absorption intensity a T may be a arithmetic mean value of the absorption intensity at a plurality of peaks in the ESR spectrum may be absorbed intensity in one of the peaks. Also, the white circles in FIG. 3 indicate the measured values when the heating temperature is 50 ° C., the white squares indicate the measured values when the heating temperature is 60 °, and the white triangles indicate the heating temperature of 65 ° C. The black circles indicate the measured values when the heating temperature is 80 ° C. The black square points indicate the measured values when the heating temperature is 80 °.
吸収強度ａＴはニトロベンゼンラジカルアニオンの濃度に比例するので、図３を用いて、各加熱温度に対応する反応速度ｋを算出し、算出した反応速度ｋから、図４に示すアレニウスプロットを作成した。図４において、横軸は温度Ｔの逆数１／Ｔ［１／Ｋ］を表し、縦軸は反応速度ｋの自然対数を表している。 Since the absorption intensity a T is proportional to the concentration of the nitrobenzene radical anion, the reaction rate k corresponding to each heating temperature was calculated using FIG. 3, and the Arrhenius plot shown in FIG. 4 was created from the calculated reaction rate k. . In FIG. 4, the horizontal axis represents the reciprocal 1 / T [1 / K] of the temperature T, and the vertical axis represents the natural logarithm of the reaction rate k.
図３および図４から、溶液Ｃを６０℃以上に加熱することで、電気分解などを行わずとも、ニトロベンゼンラジカルアニオンを製造することができるということがわかった。なお、メタノールなどのアルコールや水などの、芳香族ニトロ化合物ラジカルアニオンを破壊する作用を示す試薬（ラジカルアニオン破壊試薬）の非存在下であれば、該ラジカルアニオンが長期間安定して有機溶媒中に存在することもわかった。 From FIG. 3 and FIG. 4, it was found that the nitrobenzene radical anion can be produced by heating the solution C to 60 ° C. or higher without performing electrolysis or the like. In the absence of a reagent (radical anion-disrupting reagent) that destroys the aromatic nitro compound radical anion such as alcohol such as methanol or water, the radical anion is stable in an organic solvent for a long period of time. I also found that it exists.
また、本実施例では、芳香族ニトロ化合物としてニトロベンゼンを用いているが、ニトロベンゼンは芳香族ニトロ化合物の１つとして例示されたものに過ぎず、芳香族ニトロ化合物として、たとえば、ニトロナフタレンを用いれば、ニトロナフタレンラジカルアニオンを製造することができる。 In this example, nitrobenzene is used as the aromatic nitro compound. However, nitrobenzene is merely exemplified as one of the aromatic nitro compounds. For example, nitronaphthalene is used as the aromatic nitro compound. A nitronaphthalene radical anion can be produced.
また、本実施例では、溶液Ａおよび溶液Ｂの調製にＤＭＳＯを用いているが、ＤＭＳＯはニトロベンゼンおよび水酸化物イオンが可溶な有機溶媒の１つとして例示されたものに過ぎず、有機溶媒として、ニトロベンゼン、アセトン、アセトニトリル、テトラヒドロフラン、またはＤＭＳＯのうちのいずれか１つであるか、または、いずれか２つ以上を混合したものを用いても、ニトロベンゼンラジカルアニオンを製造することができる。 In this example, DMSO is used for the preparation of the solution A and the solution B. However, DMSO is merely exemplified as one of organic solvents in which nitrobenzene and hydroxide ions are soluble. As described above, a nitrobenzene radical anion can also be produced by using any one of nitrobenzene, acetone, acetonitrile, tetrahydrofuran, DMSO, or a mixture of any two or more thereof.
また、本実施例では、溶液Ａの調製にＴＭＡＨを用いているが、ＴＭＡＨは有機溶媒に可溶な水酸化化合物の１つとして例示されたものに過ぎず、水酸化化合物として、水酸化テトラブチルアンモニウムなどの他の水酸化テトラアルキルアンモニウムを用いても、ニトロベンゼンラジカルアニオンを製造することができる。 In this example, TMAH is used for the preparation of the solution A. However, TMAH is merely exemplified as one of the hydroxylated compounds that are soluble in an organic solvent. Nitrobenzene radical anions can also be produced using other tetraalkylammonium hydroxides such as butylammonium.
以上のようにして製造される芳香族ニトロ化合物のラジカルアニオンは、電子供与体として機能する。したがって、上記のように簡単に芳香族ニトロ化合物ラジカルアニオンを製造することで、熱エネルギーを直接電気化学エネルギーに変換および蓄積させるとともに、その電気化学エネルギーを直接電気エネルギーとして取り出せる、全く新しいタイプの化学電池の構成が可能になると考えられる。 The radical anion of the aromatic nitro compound produced as described above functions as an electron donor. Therefore, by simply producing aromatic nitro compound radical anions as described above, it is possible to convert and store thermal energy directly into electrochemical energy, and to extract the electrochemical energy directly as electrical energy. It is considered that the battery can be configured.
さらに、現在、芳香族ニトロ化合物は、医薬、農薬、染料、繊維、プラスチックスなど広範囲にわたる有機工業製品の製造における出発原料として重要であるので、芳香族ニトロ化合物のラジカルアニオンを安定に製造することは、これらの幅広い分野における各種の合成に利用できるものと期待される。 Furthermore, since aromatic nitro compounds are currently important as starting materials in the production of a wide range of organic industrial products such as pharmaceuticals, agricultural chemicals, dyes, fibers, and plastics, stable production of radical anions of aromatic nitro compounds is required. Is expected to be usable for various syntheses in these broad fields.
Claims (2)
前記第１の溶液と前記第２の溶液とを混合し、６０℃以上に加熱する第２の工程と、を含み、
前記第１の工程では、前記第１の溶液中または前記第２の溶液中にアルコールまたは水が含まれているとき、該アルコールまたは水を除去することを特徴とするニトロベンゼンまたはニトロナフタレンのラジカルアニオンの製造方法。 Whether the aromatic nitro compound of either nitrobenzene or nitronaphthalene is any one of nitrobenzene (except when the aromatic nitro compound is nitrobenzene), acetone, acetonitrile, tetrahydrofuran, or dimethyl sulfoxide; or, a first solution in an organic solvent obtained by mixing any two or more, a first step of preparing a second solution tetraalkylammonium hydroxide is dissolved in the organic solvent, the ,
Mixing the first solution and the second solution and heating to 60 ° C. or higher,
In the first step, when alcohol or water is contained in the first solution or the second solution, the alcohol or water is removed, and the radical anion of nitrobenzene or nitronaphthalene Manufacturing method.
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