JP4113955B2 - Process for producing polyfluorobenzoquinones - Google Patents
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本発明は、有機機能性材料である、２，３，５，６−テトラフルオロ−７，７，８，８−テトラシアノキノジメタンの合成中間体であり、また、医薬品、生理活性物質、農薬等に使用されるポリフルオロベンゾキノン類の簡便な製造方法に関する。 The present invention is a synthetic intermediate of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, which is an organic functional material, and includes pharmaceuticals, physiologically active substances, The present invention relates to a simple method for producing polyfluorobenzoquinones used in agricultural chemicals and the like.
従来、ポリフルオロベンゾキノン類は、対応するハイドロキノン類を原料として各種酸化反応により合成されている（例えば、非特許文献１、２参照）。しかしながら、原料となるハイドロキノン類は高価であり、塩基に対する不安定性もあって一般に収率は悪く、効率的で簡便なポリフルオロベンゾキノン類の製造方法の開発が求められていた。 Conventionally, polyfluorobenzoquinones have been synthesized by various oxidation reactions using corresponding hydroquinones as raw materials (see, for example, Non-Patent Documents 1 and 2). However, hydroquinones as raw materials are expensive, have instability with bases and generally have poor yields, and development of an efficient and simple method for producing polyfluorobenzoquinones has been demanded.
したがって、本発明は安価な原料を使用して、簡便な操作で効率良く低コストでポリフルオロベンゾキノン類を製造する方法を提供することを目的とする。 Accordingly, an object of the present invention is to provide a method for producing polyfluorobenzoquinones efficiently and at low cost by a simple operation using an inexpensive raw material.
本発明者等は鋭意検討した結果、比較的安価で入手が容易な１，４位にフッ素原子を持つポリフルオロベンゼン類を、トリフルオロ酢酸とハロゲン化炭化水素との混合溶媒中にて陽極酸化することにより、簡単な操作で効率良くポリフルオロベンゾキノン類が得られることを見出し、本発明を完成したものである。 As a result of intensive studies, the present inventors have anodically oxidized polyfluorobenzenes having fluorine atoms at positions 1 and 4 which are relatively inexpensive and easily available in a mixed solvent of trifluoroacetic acid and halogenated hydrocarbon. As a result, it has been found that polyfluorobenzoquinones can be obtained efficiently by a simple operation, and the present invention has been completed.
すなわち、本発明は次の１〜６の構成をとるものである。
１．次の一般式（１）で表されるポリフルオロベンゼンを、
That is, this invention takes the structure of the following 1-6.
1. Polyfluorobenzene represented by the following general formula (1):
（式中、Ｒ１は水素原子、ハロゲン原子、又はＯＲ２を表し、Ｒ２は炭素数１〜５のアルキル基を表す。）
トリフルオロ酢酸とハロゲン化炭化水素との混合溶媒中にて陽極酸化することを特徴とする、次の一般式（２）で表されるポリフルオロ−１、４−ベンゾキノンの製造方法：
(Wherein, R 1 represents a hydrogen atom, a halogen atom, or an OR 2, R 2 represents an alkyl group having 1 to 5 carbon atoms.)
A method for producing polyfluoro-1,4-benzoquinone represented by the following general formula (2), characterized by anodizing in a mixed solvent of trifluoroacetic acid and halogenated hydrocarbon:
（式中、Ｒ１及びＲ２は上記と同じである。）
２．ハロゲン化炭化水素が塩化メチレンであることを特徴とする１に記載のポリフルオロ−１，４−ベンゾキノンの製造方法。
３．トリフルオロ酢酸とハロゲン化炭化水素との混合割合が重量比で１０：１〜１：１、好ましくは５：１〜２：１であることを特徴とする１又は２に記載のポリフルオロ−１，４−ベンゾキノンの製造方法。
４．上記一般式（１）及び（２）において、Ｒ１がフッ素原子又はメトキシ基であることを特徴とする１〜３のいずれかに記載のポリフルオロ−１，４−ベンゾキノンの製造方法。
５．陽極酸化後、反応溶液を酸性に保持し、水を用いずに反応生成物を分離することを特徴とする１〜４のいずれかに記載のポリフルオロ−１，４−ベンゾキノンの製造方法。
(In the formula, R 1 and R 2 are the same as above.)
2. 2. The method for producing polyfluoro-1,4-benzoquinone according to 1, wherein the halogenated hydrocarbon is methylene chloride.
3. The polyfluoro-1 according to 1 or 2, wherein the mixing ratio of trifluoroacetic acid and halogenated hydrocarbon is 10: 1 to 1: 1 by weight, preferably 5: 1 to 2: 1. , 4-Benzoquinone production method.
4). In formula (1) and (2), the production method of the poly-fluoro-1,4-benzoquinone according to any one of 1 to 3, wherein the R 1 is a fluorine atom or a methoxy group.
5. 5. The method for producing polyfluoro-1,4-benzoquinone according to any one of 1 to 4, wherein the reaction solution is kept acidic after anodization and the reaction product is separated without using water.
本発明によれば、トリフルオロ酢酸とハロゲン化炭化水素との混合溶媒中にて陽極酸化を行うことにより、安価で入手が容易な１，４位にフッ素原子を有する上記一般式（１）で表されるポリフルオロベンゼン類を原料として、常温常圧下、低コスト及び簡便な操作で効率良く、上記一般式（２）で表されるポリフルオロベンゾキノン類を製造することが可能となった。
これらのポリフルオロベンゾキノン類は、有機機能性材料の合成中間体や、医薬品、生理活性物質、農薬等として幅広い用途に用いられるものであり、本発明の工業的価値は極めて高いものである。
According to the present invention, by anodizing in a mixed solvent of trifluoroacetic acid and halogenated hydrocarbon, the above general formula (1) having a fluorine atom at positions 1 and 4 which is inexpensive and easily available is provided. The polyfluorobenzoquinones represented by the above general formula (2) can be efficiently produced from the represented polyfluorobenzenes as raw materials at a low temperature and with a simple operation under normal temperature and pressure.
These polyfluorobenzoquinones are used for a wide range of applications as synthetic intermediates of organic functional materials, pharmaceuticals, physiologically active substances, agricultural chemicals, etc., and the industrial value of the present invention is extremely high.
本発明では、ポリフルオロベンゾキノン類を製造する原料として、次の一般式（１）で表されるポリフルオロベンゼンを使用する。 In the present invention, polyfluorobenzene represented by the following general formula (1) is used as a raw material for producing polyfluorobenzoquinones.
（式中、Ｒ１は水素原子、ハロゲン原子、又はＯＲ２を表し、Ｒ２は炭素数１〜５のアルキル基を表す。）
好ましいポリフルオロベンゼンとしては、例えばペンタフルオロベンゼン（Ｒ１＝Ｈ）、ヘキサフルオロベンゼン（Ｒ１＝Ｆ）、ペンタフルオロブロモベンゼン（Ｒ１＝Ｂｒ）、ペンタフルオロクロロベンゼン（Ｒ１＝Ｃｌ）、ペンタフルオロメトキシベンゼン、ペンタフルオロエトキシベンゼン、ペンタフルオロプロポキシベンゼン、ペンタフルオロブトキシベンゼン等が挙げられるが、ヘキサフルオロベンゼン及びペンタフルオロメトキシベンゼンが特に好ましい。
(In the formula, R 1 represents a hydrogen atom, a halogen atom, or OR 2 , and R 2 represents an alkyl group having 1 to 5 carbon atoms.)
Preferred polyfluorobenzenes include, for example, pentafluorobenzene (R 1 = H), hexafluorobenzene (R 1 = F), pentafluorobromobenzene (R 1 = Br), pentafluorochlorobenzene (R 1 = Cl), penta Examples include fluoromethoxybenzene, pentafluoroethoxybenzene, pentafluoropropoxybenzene, pentafluorobutoxybenzene, and the like, and hexafluorobenzene and pentafluoromethoxybenzene are particularly preferable.
これらのポリフルオロベンゼンを、トリフルオロ酢酸（以下、「ＴＦＡ」と略記することがある）とハロゲン化炭化水素との混合溶媒中で、陽極酸化することによって、１，４位にあるフッ素が脱離し、容易かつ選択的に次の一般式（２）で表されるポリフルオロ−１，４−ベンゾキノンを得ることができる。 By anodic oxidation of these polyfluorobenzenes in a mixed solvent of trifluoroacetic acid (hereinafter sometimes abbreviated as “TFA”) and halogenated hydrocarbon, fluorine at the 1 and 4 positions is removed. The polyfluoro-1,4-benzoquinone represented by the following general formula (2) can be easily and selectively obtained.
（式中、Ｒ１及びＲ２は上記と同じである。）
ＴＦＡと混合溶媒を構成するハロゲン化炭化水素としては、例えば、塩化メチレン、クロロホルム、１，２−ジクロロエタン等を使用することができるが、特に塩化メチレンを使用することが好ましい。また、ＴＦＡとハロゲン化炭化水素との混合溶媒には、所望によりアセトニトリル、酢酸、プロピオニトリル、プロピオン酸等の他の溶媒を混合してもよい。
ＴＦＡとハロゲン化炭化水素との混合割合は１０：１〜１：１、特に５：１〜２：１とすることが好ましい。
(In the formula, R 1 and R 2 are the same as above.)
As the halogenated hydrocarbon constituting the mixed solvent with TFA, for example, methylene chloride, chloroform, 1,2-dichloroethane and the like can be used, and it is particularly preferable to use methylene chloride. In addition, other solvents such as acetonitrile, acetic acid, propionitrile, propionic acid may be mixed in the mixed solvent of TFA and halogenated hydrocarbon, if desired.
The mixing ratio of TFA and halogenated hydrocarbon is preferably 10: 1 to 1: 1, particularly 5: 1 to 2: 1.
本発明で原料として使用する、上記一般式（１）で表されるポリフルオロベンゼン類はＴＦＡに対する溶解性が小さく、溶媒としてＴＦＡを単独で使用した場合には、陽極酸化反応を制御することが困難であり、また、高価なＴＦＡを多量に使用することが必要であり、製造コストが高くなるという難点があった。本発明では、ＴＦＡとハロゲン化炭化水素との混合溶媒を使用することによって、ポリフルオロベンゼン類の溶媒に対する溶解性を大幅に改善するとともに、支持電解質として使用するトリエチルアミン等の配合量の加減が容易になり、陽極酸化反応を制御することが極めて簡単になった。また、反応系の安定性が著しく改善され、反応系から生成物を安定に取得することが可能になった。 The polyfluorobenzenes represented by the general formula (1) used as a raw material in the present invention have low solubility in TFA, and when TFA is used alone as a solvent, the anodizing reaction can be controlled. It is difficult, and it is necessary to use a large amount of expensive TFA, and there is a problem that the manufacturing cost increases. In the present invention, by using a mixed solvent of TFA and halogenated hydrocarbon, the solubility of polyfluorobenzenes in a solvent is greatly improved and the amount of triethylamine used as a supporting electrolyte can be easily adjusted. As a result, it became extremely easy to control the anodizing reaction. In addition, the stability of the reaction system has been significantly improved, and it has become possible to stably obtain the product from the reaction system.
陽極酸化反応は、定電流条件下、常温常圧で常法により行なうことができる。反応生成物は塩基性条件下では不安定であり、また水への溶解度が大きいために、反応溶液を酸性に保持し、水を用いずに反応生成物を分離、精製することが好ましい。 The anodizing reaction can be carried out by a conventional method at a normal temperature and a normal pressure under a constant current condition. Since the reaction product is unstable under basic conditions and has high solubility in water, it is preferable to keep the reaction solution acidic and to separate and purify the reaction product without using water.
具体的には、例えば反応溶液を、エチルエーテル、酢酸エチル、酢酸ブチル、塩化メチレン、クロロホルム等の非水溶性有機溶媒で抽出、乾燥後、抽出溶媒を減圧下にて濃縮した後、有機残渣をカラムクロマトグラフィーにより精製することによって、目的とするポリフルオロ−１，４−ベンゾキノンを得ることができる。
精製用のカラムとしては、例えばシリカゲル、、アルミナ、セルロース等を充填したカラムを使用することができる。
Specifically, for example, the reaction solution is extracted with a water-insoluble organic solvent such as ethyl ether, ethyl acetate, butyl acetate, methylene chloride, and chloroform, dried, the extraction solvent is concentrated under reduced pressure, and then the organic residue is removed. The target polyfluoro-1,4-benzoquinone can be obtained by purification by column chromatography.
As the column for purification, for example, a column packed with silica gel, alumina, cellulose or the like can be used.
つぎに、実施例により本発明をさらに説明するが、以下の具体例は本発明を限定するものではない。
以下の実施例では、図１（模式図）にみられるような、ビーカー型セル（電解装置）を使用して、ポリフルオロベンゼンの陽極酸化反応を行った。このビーカー型セル１は、白金板で構成した陰極２及び陽極３、温度計４を具備するもので、陰極２側には素焼円筒型隔膜５を設けるとともに、撹拌子６を備えている。
EXAMPLES Next, the present invention will be further described with reference to examples, but the following specific examples are not intended to limit the present invention.
In the following examples, an anodizing reaction of polyfluorobenzene was performed using a beaker type cell (electrolytic device) as shown in FIG. 1 (schematic diagram). The beaker-type cell 1 includes a cathode 2 and an
（実施例１）
基質にヘキサフルオロベンゼン［一般式（１）でＲ１＝Ｆ］１０ｍｍｏｌ、支持電解質としてトリエチルアミン６０ｍｍｏｌ、陽陰極に白金板（陽極７ｃｍｘ４ｃｍ、陰極２ｘ１ｃｍ）、陰極に素焼円筒型隔膜を備え付けた５０ｍｌビーカー型セルを用い、溶媒にトリフルオロ酢酸と塩化メチレンの混合溶媒４０ｍｌ（体積比５：１）を調製して陽極側に３０ｍｌ、陰極側に１０ｍｌ加え、定電流電解（電流密度１０ｍＡ／ｃｍ２）を行った。２Ｆ／ｍｏｌの通電後、反応溶液に水２００ｍｌを加えて３０分攪拌してジエチルエーテル１００ｍｌで５回抽出し、無水硫酸マグネシウムで乾燥させ、溶媒を留去した。生成物が塩基に非常に弱いため、真空ポンプ及びショートカラムによりトリフルオロ酢酸を除去し、これを再度カラムクロマトグラフィーで精製後、テトラフルオロベンゾキノン［一般式（２）でＲ１＝Ｆ］を８２％の収率で得た。生成物の確認は、次の物性値により行った。
13C-NMR(100 MHz, acetone-d6)：δ144.1(dm, JC,F = 278.3 Hz), 172.1−172.8(m)ppm，FT-IR(KBr) 1690, 1674, 1326, 1045, 1011, 737, 447 and 423 cm−1，EI-MS：m/z 180(M+)，m.p. 185−187 ℃(lit. m.p. 179 ℃)
(Example 1)
Substrates hexafluorobenzene [formula (1) in R 1 = F] 10 mmol, triethylamine 60mmol as a supporting electrolyte, a platinum plate explicitly cathode (anode 7Cmx4cm, cathode 2X1cm), 50 ml beaker type equipped with a biscuit cylindrical diaphragm to the cathode Using a cell, 40 ml of a mixed solvent of trifluoroacetic acid and methylene chloride (volume ratio 5: 1) was prepared as a solvent, 30 ml on the anode side and 10 ml on the cathode side were added, and constant current electrolysis (current density 10 mA / cm 2 ) was performed. went. After energization at 2 F / mol, 200 ml of water was added to the reaction solution, stirred for 30 minutes, extracted five times with 100 ml of diethyl ether, dried over anhydrous magnesium sulfate, and the solvent was distilled off. Since the product is very weak bases, the trifluoroacetic acid was removed by vacuum pumps and short column, after purification by re column chromatography [in the general formula (2) R 1 = F] tetrafluoro-benzoquinone 82 % Yield. The product was confirmed by the following physical property values.
13 C-NMR (100 MHz, acetone-d 6 ): δ 144.1 (dm, J C, F = 278.3 Hz), 172.1-172.8 (m) ppm, FT-IR (KBr) 1690, 1674, 1326, 1045 , 1011, 737, 447 and 423 cm −1 , EI-MS: m / z 180 (M + ), mp 185−187 ℃ (lit. mp 179 ℃)
（実施例２）
実施例１において、基質としてペンタフルオロメトキシベンゼン［一般式（１）でＲ１＝ＯＭｅ］１０ｍｍｏｌを使用した以外は実施例１と同様に処理し、トリフルオロメトキシベンゾキノン［一般式（２）でＲ１＝ＯＭｅ］を８１％の収率で得た。生成物の確認は、次の物性値により行った。
1H-NMR(400 MHz, CDCl3)：δ4.23 ppm(3H, d, JCH3,F = 4.4 Hz)，FT-IR(KBr) 1697, 1645, 1469, 1297, 1200, 1118, 668, 576, and 438 cm−1，EI-MS：m/z 192(M+)，m.p. 154−158 ℃(lit. m.p. 159−161.5 ℃)
(Example 2)
In Example 1, treatment was performed in the same manner as in Example 1 except that 10 mmol of pentafluoromethoxybenzene [R 1 = OMe in the general formula (1)] was used as a substrate, and trifluoromethoxybenzoquinone [R in the general formula (2) 1 = OMe] was obtained in 81% yield. The product was confirmed by the following physical property values.
1 H-NMR (400 MHz, CDCl 3 ): δ4.23 ppm (3H, d, J CH3, F = 4.4 Hz), FT-IR (KBr) 1697, 1645, 1469, 1297, 1200, 1118, 668, 576, and 438 cm −1 , EI-MS: m / z 192 (M + ), mp 154–158 ° C (lit. mp 159–161.5 ° C)
（実施例３）
実施例１において、基質としてペンタフルオロベンゼン［一般式Ｒ１＝Ｈ］１０ｍｍｏｌを使用した以外は実施例１と同様に処理し、トリフルオロベンゾキノン［一般式（２）でＲ１＝Ｈ］を５５％の収率で得た。生成物の確認は、次の物性値により行った。
1H-NMR(400 MHz, CDCl3)：δ6.49 ppm(1H, q, JH,F = 8.0 Hz)，13C-NMR(67.8 MHz, DMSO)：δ112.5(d, JC,F = 16.8 Hz), 143.8(dm, JC,F = 278.1 Hz), 159.6(d, JC,F = 148.3 Hz), 171.5−172.3(m) and 178.0−178.6(m)，FT-IR(KBr) 1684, 1645, 1506, 1302, 1211, 1165, 1060, 955, 872, 778, 721 and 419cm−1，EI-MS：m/z 162(M+)，m.p. 142−146 ℃(lit. m.p. 148−149℃)
(Example 3)
In Example 1, except for using pentafluorobenzene [formula R 1 = H] 10 mmol as the substrate was treated in the same manner as in Example 1, [in the general formula (2) R 1 = H] trifluoro-benzoquinone 55 % Yield. The product was confirmed by the following physical property values.
1 H-NMR (400 MHz, CDCl 3 ): δ 6.49 ppm (1H, q, J H, F = 8.0 Hz), 13 C-NMR (67.8 MHz, DMSO): δ 112.5 (d, J C, F = 16.8 Hz), 143.8 (dm, J C, F = 278.1 Hz), 159.6 (d, J C, F = 148.3 Hz), 171.5-172.3 (m) and 178.0-178.6 (m), FT-IR ( KBr) 1684, 1645, 1506, 1302, 1211, 1165, 1060, 955, 872, 778, 721 and 419 cm −1 , EI-MS: m / z 162 (M + ), mp 142−146 ℃ (lit. mp (148-149 ° C)
（実施例４）
実施例１において、基質としてペンタフルオロブロモベンゼン［一般式（１）でＲ１＝Ｂｒ］１０ｍｍｏｌを使用した以外は実施例１と同様に処理し、トリフルオロブロモベンゾキノン［一般式（２）でＲ１＝Ｂｒ］を５１％の収率で得た。生成物の確認は、次の物性値により行った。
13C-NMR(67.8 MHz,DMSO)：δ112.8(d, JC,F = 15.6Hz), 143.6(dm, JC,F = 278.0 Hz), 154.9(d, JC,F = 280.3Hz), 169.1−169.9(m), 172.2−172.4(m)ppm，FT-IR(KBr) 1697, 1633, 1507, 1328, 1282, 835, 732 and 582cm−1，EI-MS：m/z 240(M+), 242(M+2)，m.p. 128−132 ℃
Example 4
In Example 1, treatment was carried out in the same manner as in Example 1 except that 10 mmol of pentafluorobromobenzene [R 1 = Br in general formula (1)] was used as a substrate, and trifluorobromobenzoquinone [R in general formula (2) 1 = Br] was obtained in 51% yield. The product was confirmed by the following physical property values.
13 C-NMR (67.8 MHz, DMSO): δ 112.8 (d, J C, F = 15.6 Hz), 143.6 (dm, J C, F = 278.0 Hz), 154.9 (d, J C, F = 280.3 Hz) ), 169.1-169.9 (m), 172.2-172.4 (m) ppm, FT-IR (KBr) 1697, 1633, 1507, 1328, 1282, 835, 732 and 582cm −1 , EI-MS: m / z 240 ( M + ), 242 (M + 2), mp 128-132 ℃
１ ビーカー型セル
２ 陰極
３ 陽極
４ 温度計
５ 素焼円筒型隔膜
６ 撹拌子
1 Beaker type cell 2
Claims (5)
トリフルオロ酢酸とハロゲン化炭化水素との混合溶媒中にて陽極酸化することを特徴とする、次の一般式（２）で表されるポリフルオロ−１、４−ベンゾキノンの製造方法：
A method for producing polyfluoro-1,4-benzoquinone represented by the following general formula (2), characterized by anodizing in a mixed solvent of trifluoroacetic acid and halogenated hydrocarbon:
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| JP2004147589A JP4113955B2 (en) | 2004-05-18 | 2004-05-18 | Process for producing polyfluorobenzoquinones |
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