JP2006191947A - Method for dehalogenation of organic halides - Google Patents
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Abstract
【課題】 電解質や還元剤を用いることなく、ビタミンＢ12化合物を用いて有機ハロゲン化物を脱ハロゲン化しうる方法を提供する。
【解決手段】 本発明の脱ハロゲン化方法は、有機ハロゲン化物を光照射下、固体光触媒の存在下に、ビタミンＢ12化合物と接触させることを特徴とする。例えばビタミンＢ12、ビタミンＢ12誘導体（Ｉ）
を用いる。溶媒中で接触させる。光触媒は光触媒酸化チタンである。基材上に担持された固体光触媒に、ビタミンＢ12化合物が担持されてなる脱ハロゲン化触媒を用いる。
【選択図】 なしPROBLEM TO BE SOLVED: To provide a method capable of dehalogenating an organic halide using a vitamin B 12 compound without using an electrolyte or a reducing agent.
The dehalogenation method of the present invention is characterized in that an organic halide is brought into contact with a vitamin B 12 compound in the presence of a solid photocatalyst under light irradiation. For example, vitamin B 12 and vitamin B 12 derivative (I)
Is used. Contact in solvent. The photocatalyst is photocatalytic titanium oxide. A dehalogenation catalyst in which a vitamin B 12 compound is supported on a solid photocatalyst supported on a substrate is used.
[Selection figure] None
Description
本発明は、有機ハロゲン化物の脱ハロゲン化方法に関する。 The present invention relates to a method for dehalogenation of an organic halide.
有機ハロゲン化物を還元的に脱ハロゲン化する方法として、ビタミンＢ12化合物を電解触媒として用いたり、電極上にビタミンＢ12化合物を担持した修飾電極を用いて、電解質溶液中で電解還元する方法が知られているが〔非特許文献１：H.Shimakoshi, et.al, Dalton Trans., 878(2004)、非特許文献２：H.Shimakoshi, et.al, Dalton Trans., 2308(2003)、非特許文献３：H.Shimakoshi, et.al, Chem.Commun., 50(2004)〕、かかる方法では、電解質溶液に導電性を与えるために、大量の電解質を用いる必要があった。 The organic halide as a method for reductively dehalogenated, or with vitamin B 12 compound as electrocatalyst, using a modified electrode carrying a vitamin B 12 compound on the electrode, a method of electrolytic reduction in an electrolytic solution [Non-patent document 1: H. Shimakoshi, et.al, Dalton Trans., 878 (2004), Non-patent document 2: H. Shimakoshi, et.al, Dalton Trans., 2308 (2003), Non-Patent Document 3: H. Shimakoshi, et.al, Chem. Commun., 50 (2004)], this method requires the use of a large amount of electrolyte in order to impart conductivity to the electrolyte solution.
電解質を用いることなく、有機ハロゲン化物を脱ハロゲン化する方法として、本発明者らは、すでに、有機ハロゲン化物を光照射下、ルテニウム(II)トリスビピリジン錯体と、トリエタノールアミンなどの還元剤との存在下にビタミンＢ12化合物と接触させる方法を提案している〔非特許文献４：H.Shimakoshi, et.al, Chem.Commun., 1806(2004)〕。しかし、この方法は、還元剤を必要とするものであった。 As a method for dehalogenating an organic halide without using an electrolyte, the present inventors have already obtained a ruthenium (II) trisbipyridine complex and a reducing agent such as triethanolamine under irradiation of the organic halide with light. Has proposed a method of contacting with a vitamin B 12 compound in the presence of non-patent document 4: Non-patent document 4: H. Shimakoshi, et.al, Chem. Commun., 1806 (2004)]. However, this method requires a reducing agent.
そこで本発明者は、電解質や還元剤を用いることなく、ビタミンＢ12化合物を用いて有機ハロゲン化物を還元的に脱ハロゲン化しうる方法を開発するべく鋭意検討した結果、固体光触媒の存在下では、電解質や還元剤がなくても、光照射下、有機ハロゲン化物がビタミンＢ12化合物と接触することにより、脱ハロゲン化することを見出し、本発明に至った。 Therefore, the present inventor has intensively studied to develop a method capable of reductively dehalogenating an organic halide using a vitamin B 12 compound without using an electrolyte or a reducing agent. As a result, in the presence of a solid photocatalyst, Even without an electrolyte or a reducing agent, the present inventors have found that dehalogenation occurs when an organic halide comes into contact with a vitamin B 12 compound under light irradiation, and the present invention has been achieved.
すなわち本発明は、有機ハロゲン化物を光照射下、固体光触媒の存在下に、ビタミンＢ12化合物と接触させることを特徴とする前記有機ハロゲン化物の脱ハロゲン化方法を提供するものである。 That is, the present invention provides a method for dehalogenating an organic halide, characterized in that the organic halide is brought into contact with a vitamin B 12 compound in the presence of light and in the presence of a solid photocatalyst.
本発明の脱ハロゲン化方法によれば、電解質や還元剤を使用することなく、有機ハロゲン化物を脱ハロゲン化することができる。 According to the dehalogenation method of the present invention, an organic halide can be dehalogenated without using an electrolyte or a reducing agent.
本発明の脱ハロゲン化方法に適用される有機ハロゲン化物は、フッソ原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子を有する有機化合物であって、例えば１，１−ビス（４−クロロフェニル）−２，２，２−トリクロロエタン〔ＤＤＴ〕、２−ブロモエチルベンゼン、２−クロロエチルベンゼン、臭化ベンジル、塩化ベンジルなどのハロゲン化芳香族炭化水素、クロロホルム、塩化メチレン、四塩化炭素、フルオロトリクロロメタン、１，１，１−トリクロロメタン、ブロモホルム、１−ブロモプロパン、２−ブロモプロパン、臭化アリル、塩化アリル、ヨウ化メチルなどのハロゲン化炭化水素などが挙げられる。 The organic halide applied to the dehalogenation method of the present invention is an organic compound having a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, for example, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane [DDT], 2-bromoethylbenzene, 2-chloroethylbenzene, benzyl bromide, halogenated aromatic hydrocarbons such as benzyl chloride, chloroform, methylene chloride, carbon tetrachloride, fluorotrichloromethane, Examples thereof include halogenated hydrocarbons such as 1,1,1-trichloromethane, bromoform, 1-bromopropane, 2-bromopropane, allyl bromide, allyl chloride, and methyl iodide.
固体光触媒とは、光を照射されることにより、触媒活性を示す固体であり、紫外光を照射されることにより触媒活性を示す紫外光応答型の光触媒であってもよいが、紫外光ではビタミンＢ12化合物を分解するおそれがあることから、可視光を照射されることにより触媒活性を示す可視光応答型の光触媒が好ましく用いられる。固体光触媒としては、光を照射されることにより−０．３Ｖ（ｖｓＮＨＥ、ｐＨ７．０ Ｈ2Ｏ）以下の還元電位を示して、ビタミンＢ12化合物のコバルト原子（Ｃｏ）を１価に還元することのできるものが用いられ、入手が比較的容易で、光照射下に−０．５Ｖ（ｖｓＮＨＥ、ｐＨ７．０ Ｈ2Ｏ）以下の還元電位を示すことから、酸化チタンからなる光触媒酸化チタンが好ましく用いられる。光触媒酸化チタンとしては、通常、結晶性のもの、例えばアナターゼ型、ルチル型、アナターゼ・ルチル型、ブルッカイト型の酸化チタンなどが用いられる。 A solid photocatalyst is a solid that exhibits catalytic activity when irradiated with light, and may be an ultraviolet light-responsive photocatalyst that exhibits catalytic activity when irradiated with ultraviolet light. Since there is a possibility of decomposing the B 12 compound, a visible light responsive photocatalyst that exhibits catalytic activity when irradiated with visible light is preferably used. The solid photocatalyst exhibits a reduction potential of −0.3 V (vsNHE, pH 7.0 H 2 O) or less when irradiated with light, and reduces the cobalt atom (Co) of the vitamin B 12 compound to monovalent. Can be used, is relatively easy to obtain, and shows a reduction potential of −0.5 V (vsNHE, pH 7.0 H 2 O) or less under light irradiation. Preferably used. As the photocatalytic titanium oxide, crystalline ones such as anatase type, rutile type, anatase / rutile type, brookite type titanium oxide and the like are usually used.
このような光触媒酸化チタンとしては、例えば特許文献１〔特開２００１−７２４１９号公報〕、特許文献２〔特開２００１−３１６１１６号公報〕、特許文献３〔特開２００２−９７０１９号公報〕に開示されている粉末状のものを挙げることができる。また、市販の光触媒酸化チタンを用いることもでき、具体的には、「ＴＰ−Ｓ２０１」（住友化学(株)製）、「ＳＴ−０１」（石原産業(株)製）、「ＳＴ−２１」（石原産業(株)製）、「ＴＫＰ-１０１」（テイカ(株)製）、「ＡＫＴ−６００」（テイカ(株)製）、「ＭＴ−１５０Ａ」（テイカ(株)製）、「Ｐ−２５」（日本エアロジル(株)製）などとして市販されている粉末状のものが挙げられる。 Examples of such photocatalytic titanium oxide are disclosed in, for example, Patent Document 1 (Japanese Patent Laid-Open No. 2001-72419), Patent Document 2 (Japanese Patent Laid-Open No. 2001-316116), and Patent Document 3 (Japanese Patent Laid-Open No. 2002-97019). The powdery thing currently mentioned can be mentioned. Commercially available photocatalytic titanium oxide can also be used. Specifically, “TP-S201” (manufactured by Sumitomo Chemical Co., Ltd.), “ST-01” (manufactured by Ishihara Sangyo Co., Ltd.), “ST-21” "(Ishihara Sangyo Co., Ltd.)," TKP-101 "(Taika Co., Ltd.)," AKT-600 "(Taika Co., Ltd.)," MT-150A "(Taika Co., Ltd.)," P-25 "(manufactured by Nippon Aerosil Co., Ltd.) and the like are commercially available.
固体光触媒は、粉末状で用いられてもよいが、脱ハロゲン化後の反応混合物から容易に取り出すことができる形状に成形されていることが好ましく、例えば通常の造粒方法により造粒されていてもよい。 The solid photocatalyst may be used in the form of powder, but is preferably shaped into a shape that can be easily taken out from the reaction mixture after dehalogenation, for example, granulated by a normal granulation method. Also good.
また、固体光触媒は、反応混合物から容易に取り出すことのできる形状の基材に担持されていることが好ましい。基材としては、例えば有機ハロゲン化物、固体光触媒、ビタミンＢ12化合物および溶媒に対して不活性なものであればよく、例えば無機ガラス、アルミナなどのセラミックス、白金、金などの金属などが挙げられる。基材の形状は、脱ハロゲン化後の混合物から取り出し易いものであればよく、例えば板状、球状、リング状、網状の基材が用いられる。 Moreover, it is preferable that the solid photocatalyst is supported on a base material having a shape that can be easily taken out from the reaction mixture. The substrate may be any material that is inert to organic halides, solid photocatalysts, vitamin B 12 compounds and solvents, and examples thereof include inorganic glass, ceramics such as alumina, metals such as platinum and gold. . The shape of the substrate is not particularly limited as long as it can be easily taken out from the mixture after dehalogenation. For example, a plate-like, spherical, ring-like, or net-like substrate is used.
固体光触媒を基材上に担持するには、例えば粉末状の固体光触媒をバインダーと共に揮発性の溶媒に分散させたコーティング液を基材上に塗布し、溶媒を揮発させればよい。コーティング液に用いうる溶媒としては、例えばエタノールなどのアルコール類、水などが挙げられる。このようなコーティング液として一般に入手可能なものを用いることもでき、例えば「ＴＳ−Ｓ４１１０」（住友化学(株)製）、「ＴＣ−Ｓ４１１５」（住友化学(株)製）、「ＴＫＣ−３０３」（テイカ(株)製）、「ＴＫＣ−３０４」（テイカ(株)製）などが挙げられる。溶媒を揮発させることにより、バインダーにより粉末状の固体光触媒が基材上に担持される。バインダーの種類によっては、溶媒を揮発させた後、加熱してもよい。 In order to carry the solid photocatalyst on the substrate, for example, a coating liquid in which a powdery solid photocatalyst is dispersed in a volatile solvent together with a binder may be applied on the substrate, and the solvent may be volatilized. Examples of the solvent that can be used for the coating liquid include alcohols such as ethanol, water, and the like. As such a coating liquid, generally available ones can be used. For example, “TS-S4110” (manufactured by Sumitomo Chemical Co., Ltd.), “TC-S4115” (manufactured by Sumitomo Chemical Co., Ltd.), “TKC-303”. "(Manufactured by Teika)," TKC-304 "(manufactured by Teika), and the like. By volatilizing the solvent, the powdery solid photocatalyst is supported on the substrate by the binder. Depending on the type of the binder, the solvent may be volatilized and then heated.
ビタミンＢ12化合物とは、ビタミンＢ12骨格を有する化合物であり、ビタミンＢ12（シアノコバラミン）の他、例えば式（Ｉ）
で示されるビタミンＢ12関連化合物などが挙げられる。
The vitamin B 12 compound is a compound having a vitamin B 12 skeleton. In addition to vitamin B 12 (cyanocobalamin), for example, the formula (I)
And vitamin B 12 related compounds represented by
式（Ｉ）において、Ｒ1〜Ｒ7におけるアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基などの炭素数１〜８程度のアルキル基が挙げられ、通常はメチル基である。 In the formula (I), examples of the alkyl group in R 1 to R 7 include an alkyl group having about 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group, and is usually a methyl group. .
固体光触媒およびビタミンＢ12化合物は、それぞれ単独で本発明の脱ハロゲン化方法に用いられてもよいが、固体光触媒にビタミンＢ12化合物を担持させた脱ハロゲン化触媒として用いることが、より速やかに有機ハロゲン化物を脱ハロゲン化し得、また脱ハロゲン化後の反応混合物から固体光触媒と同時にビタミンＢ12化合物を回収し得る点で、好ましい。 The solid photocatalyst and the vitamin B 12 compound may each be used alone in the dehalogenation method of the present invention. However, the solid photocatalyst and the vitamin B 12 compound can be used more quickly as a dehalogenation catalyst in which the vitamin B 12 compound is supported on the solid photocatalyst. It is preferable in that the organic halide can be dehalogenated and the vitamin B 12 compound can be recovered simultaneously with the solid photocatalyst from the reaction mixture after dehalogenation.
ビタミンＢ12化合物を固体光触媒に担持するには、例えば揮発性の溶媒中でビタミンＢ12化合物を固体光触媒と混合して接触させたのち、溶媒を除去すればよい。ビタミンＢ12の担持に用いうる溶媒としては、ビタミンＢ12化合物および固体光触媒に対して不活性なもの、好ましくはビタミンＢ12化合物を溶解しうるものが用いられ、具体的には、例えばメタノール、エタノール、プロパノールなどのアルコール類、アセトンなどのケトン類、ベンゼン、トルエンなどの芳香族炭化水素類などが用いられる。接触は通常、攪拌下に行われる。接触させることにより、ビタミンＢ12化合物が固体光触媒上に担持されて、目的の脱ハロゲン化触媒を得ることができる。接触後、通常は濾過操作により、ビタミンＢ12化合物が担持された固体光触媒を得ることができる。 In order to carry the vitamin B 12 compound on the solid photocatalyst, for example, the vitamin B 12 compound is mixed with the solid photocatalyst in a volatile solvent and brought into contact, and then the solvent is removed. As the solvent usable in carrying vitamin B 12, it is inert relative to vitamin B 12 compound and a solid photocatalyst, preferably used are those capable of dissolving the vitamin B 12 compounds, specifically, for example, methanol, Alcohols such as ethanol and propanol, ketones such as acetone, and aromatic hydrocarbons such as benzene and toluene are used. Contact is usually carried out with stirring. By contacting, the vitamin B 12 compound is supported on the solid photocatalyst, and the desired dehalogenation catalyst can be obtained. After the contact, a solid photocatalyst carrying a vitamin B 12 compound can be obtained usually by filtration.
また、固体光触媒として基材上に担持されたものを用いる場合には、例えば基材上に固体光触媒を担持させた後、ビタミンＢ12化合物を揮発性の溶媒で希釈して塗布し、溶媒を揮発させればよい。溶媒を揮発させることにより、基材上に担持された固体光触媒に、さらにビタミンＢ12化合物が析出して担持され、目的の脱ハロゲン化触媒を得ることができる。 When using a solid photocatalyst supported on a base material, for example, after supporting the solid photocatalyst on the base material, the vitamin B 12 compound is diluted with a volatile solvent and applied. It only has to be volatilized. By volatilizing the solvent, the vitamin B 12 compound is further deposited and supported on the solid photocatalyst supported on the substrate, and the desired dehalogenation catalyst can be obtained.
本発明の脱ハロゲン化方法により有機ハロゲン化物を脱ハロゲン化するには、例えば溶媒中で、有機ハロゲン化物、固体光触媒およびビタミンＢ12化合物を混合することにより、固体光触媒の存在下に有機ハロゲン化物をビタミンＢ12化合物と接触させ、光を照射すればよい。ビタミンＢ12化合物として、固体光触媒にビタミンＢ12が担持された脱ハロゲン化触媒を用いる場合には、溶媒中で有機ハロゲン化物を脱ハロゲン化触媒と混合し、光を照射すればよい。 In order to dehalogenate an organic halide by the dehalogenation method of the present invention, for example, by mixing an organic halide, a solid photocatalyst and a vitamin B 12 compound in a solvent, the organic halide is present in the presence of the solid photocatalyst. May be brought into contact with the vitamin B 12 compound and irradiated with light. As vitamin B 12 compound, in the case of using a dehalogenation catalyst vitamin B 12 is supported on a solid photocatalyst, the organic halide is mixed with dehalogenation catalyst in a solvent, it may be irradiated with light.
本発明の脱ハロゲン化方法に用いうる溶媒としては、有機ハロゲン化物およびビタミンＢ12化合物に対して不活性なもの、例えばメタノール、エタノール、プロパノールなどのアルコール類、アセトンなどのケトン類、ベンゼン、トルエンなどの芳香族炭化水素類などが挙げられ、好ましくはアルコール類、さらに好ましくはエタノールである。 Solvents that can be used in the dehalogenation method of the present invention include those inert to organic halides and vitamin B 12 compounds, such as alcohols such as methanol, ethanol, and propanol, ketones such as acetone, benzene, and toluene. Aromatic hydrocarbons such as, and the like, and alcohols are preferable, and ethanol is more preferable.
ビタミンＢ12化合物の使用量は、有機ハロゲン化物に対して、通常０．００２モル倍〜０．０１モル倍程度であり、固体光触媒の使用量は、ビタミンＢ12化合物に対して通常１０質量倍〜２０質量倍程度であり、溶媒の使用量は有機ハロゲン化物、固体光触媒およびビタミンＢ12化合物の合計量に対して、通常１００質量倍〜１０００質量倍程度、好ましくは５００質量倍〜６００質量倍程度である。 The amount of vitamin B 12 compound, the organic halide is usually 0.002 mol times to 0.01 moles per mol, the amount of the solid photocatalysts is usually 10 times by mass relative to vitamin B 12 compound is about 20 times by mass, the amount of the solvent is an organic halide, the total amount of the solid photocatalytic and vitamin B 12 compound, usually 100 times by mass to 1000 times by mass, preferably about 500 times by mass to 600 mass times Degree.
照射する光は、固体光触媒として紫外光応答型の光触媒を用いた場合には紫外光が、可視光応答型の光触媒を用いた場合には可視光が、それぞれ用いられる。 As the light to be irradiated, ultraviolet light is used when an ultraviolet light responsive photocatalyst is used as the solid photocatalyst, and visible light is used when a visible light responsive photocatalyst is used.
脱ハロゲン化温度は、通常２０℃〜４０℃、好ましくは３０℃〜３５℃程度である。脱ハロゲン化に要する時間は、通常３時間〜２４時間程度である。 The dehalogenation temperature is usually about 20 ° C to 40 ° C, preferably about 30 ° C to 35 ° C. The time required for dehalogenation is usually about 3 to 24 hours.
ビタミンＢ12化合物において、中心金属原子であるコバルト原子は通常、３価であるが、固体光触媒の存在下に光を照射すると、固体光触媒の還元作用によって１価に還元される。コバルト原子が１価に還元されたビタミンＢ12化合物は、高い還元力を示すので、本発明の脱ハロゲン化方法では、かかるビタミンＢ12化合物が、有機ハロゲン化物に作用して還元し、脱ハロゲン化するものと考えられる。 In the vitamin B 12 compound, the cobalt atom as the central metal atom is usually trivalent, but when irradiated with light in the presence of the solid photocatalyst, it is reduced to monovalent by the reducing action of the solid photocatalyst. Since the vitamin B 12 compound in which the cobalt atom is reduced to a monovalent value exhibits a high reducing power, in the dehalogenation method of the present invention, the vitamin B 12 compound acts on the organic halide to reduce it, and dehalogenates. It is thought that
脱ハロゲン化後の固体光触媒およびビタミンＢ12化合物は、反応混合物から回収して、再利用することができる。ビタミンＢ12化合物を固体光触媒に担持させて脱ハロゲン化触媒として用いた場合には、濾過操作などの通常の固液分離操作により、容易に、反応混合物から回収することができて、好ましい。また、固体光触媒を成形して用いたり、基材に担持させて用いた場合には、さらに容易に、脱ハロゲン化後の反応混合物から回収することができるので、好ましい。 The solid photocatalyst and vitamin B 12 compound after dehalogenation can be recovered from the reaction mixture and reused. When a vitamin B 12 compound is supported on a solid photocatalyst and used as a dehalogenation catalyst, it can be easily recovered from the reaction mixture by a normal solid-liquid separation operation such as filtration, which is preferable. Further, when the solid photocatalyst is used after being shaped or supported on a substrate, it can be recovered from the reaction mixture after dehalogenation more easily, which is preferable.
以下、実施例により本発明をより詳細に説明するが、本発明は、かかる実施例により限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
実施例１
〔脱ハロゲン化触媒の調製〕
式（Ｉ）におけるＲ1〜Ｒ7が水素原子であり、Ｘがシアノ基であるビタミンＢ12誘導体（コビリン酸）１３ｍｇをエタノール〔和光純薬工業(株)製、試薬特級〕１．１ｇに溶解させ、アナターゼ型酸化チタン粉末〔石原産業(株)製、「ＳＴ−２１」〕０．１５ｇを加え、室温（約２５℃）にて２４時間撹拌した後、固形分を濾取し、乾燥させて、アナターゼ型酸化チタン粉末に上記ビタミンＢ12誘導体（コビリン酸）が担持された脱ハロゲン化触媒を得た。この脱ハロゲン化触媒のビタミンＢ12誘導体の担持量は、アナターゼ型酸化チタン粉末の単位表面積あたりで７．０×１０-11モル／ｃｍ2であり、単位質量あたりで５２ｍｇ／ｇであった。
Example 1
(Preparation of dehalogenation catalyst)
In formula (I), 13 mg of vitamin B 12 derivative (cobilic acid) in which R 1 to R 7 are hydrogen atoms and X is a cyano group was added to 1.1 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) Dissolve and add 0.15 g of anatase-type titanium oxide powder [Ishihara Sangyo Co., Ltd., “ST-21”] and stir at room temperature (about 25 ° C.) for 24 hours. Thus, a dehalogenation catalyst in which the vitamin B 12 derivative (cobyrinic acid) was supported on anatase-type titanium oxide powder was obtained. The amount of the vitamin B 12 derivative supported on the dehalogenation catalyst was 7.0 × 10 −11 mol / cm 2 per unit surface area of the anatase-type titanium oxide powder and 52 mg / g per unit mass.
この脱ハロゲン化触媒は、Ｃｏ(III)を示す赤色を呈しており、ＭＡＬＤＩ−ＴＯＦ−ＭＳ測定を行ったところ、上記ビタミンＢ12誘導体（コビリン酸）に由来するｍ／ｚ＝９３８およびｍ／ｚ＝９４６のピークが観測された。この脱ハロゲン化触媒をエタノールと混合し、ブラックライト〔フナコシ(株)製、１５Ｗ〕により紫外光を１時間照射したところ、Ｃｏ(Ｉ)を示す緑色を呈した。 This dehalogenation catalyst has a red color indicating Co (III), and MALDI-TOF-MS measurement showed that m / z = 938 and m / z derived from the vitamin B 12 derivative (cobyrinic acid). A peak at z = 946 was observed. When this dehalogenation catalyst was mixed with ethanol and irradiated with ultraviolet light with a black light (Funakoshi Co., Ltd., 15 W) for 1 hour, a green color indicating Co (I) was obtained.
〔有機ハロゲン化物の脱ハロゲン化〕
第１表に示す有機ハロゲン化物を３ミリモル／Ｌ（３ｍｍｏｌ／Ｌ）の濃度でエタノールに溶解させ、３０ｍＬを秤取り、石英ガラス製セルに入れた。次いで、上記で得た脱ハロゲン化触媒２０ｍｇを加え、撹拌して懸濁させながら窒素ガスをバブリングさせて溶存酸素を除去し、次いで攪拌下にブラックライト〔フナコシ(株)製、１５Ｗ〕により、反応セル外表面における紫外光強度１．７６ｍＷ／ｃｍ2で紫外光を２４時間照射した。紫外光照射後の反応混合物における有機ハロゲン化物の含有量をガスクロマトグラフィーにより求めて、用いた有機ハロゲン化物のうち脱ハロゲン化されたものの割合（転化率、％）を求めた。結果を第１表に示す。
[Dehalogenation of organic halides]
The organic halides shown in Table 1 were dissolved in ethanol at a concentration of 3 mmol / L (3 mmol / L), 30 mL was weighed and placed in a quartz glass cell. Next, 20 mg of the above-obtained dehalogenation catalyst was added, and nitrogen gas was bubbled while suspended by stirring to remove dissolved oxygen. Then, under stirring, black light (manufactured by Funakoshi Co., Ltd., 15 W) was used. Ultraviolet light was irradiated for 24 hours at an ultraviolet light intensity of 1.76 mW / cm 2 on the outer surface of the reaction cell. The content of the organic halide in the reaction mixture after irradiation with ultraviolet light was determined by gas chromatography, and the proportion of the dehalogenated organic halide (conversion rate,%) was determined. The results are shown in Table 1.
第 １ 表
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
試験 有機ハロゲン化物 転化率 番号 （％）
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
１ ２−ブロモエチルベンゼン ９５
２ １，１−ビス（４−クロロフェニル）−２，２，２−トリクロロエタン ９９
３ 臭化ベンジル １００
４ 塩化ベンジル ９９
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Table 1
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Test Organic Halide Conversion Number (%)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
1 2-Bromoethylbenzene 95
2 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane 99
3 Benzyl bromide 100
4 Benzyl chloride 99
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例２
〔脱ハロゲン化触媒の調製〕
アナターゼ型酸化チタン粉末に代えて、ルチル型酸化チタン粉末〔テイカ(株)製、「ＭＴ−１５０Ａ」〕０．１５ｇを用いた以外は実施例１と同様に操作して、脱ハロゲン化触媒を得た。この脱ハロゲン化触媒のビタミンＢ12誘導体の担持量は、ルチル型酸化チタン粉末の単位表面積あたりで７．０×１０-11モル／ｃｍ2であり、単位質量あたりで５４ｍｇ／ｇであった。
Example 2
(Preparation of dehalogenation catalyst)
A dehalogenation catalyst was prepared in the same manner as in Example 1, except that 0.15 g of rutile type titanium oxide powder [manufactured by Teika Co., Ltd., “MT-150A”] was used instead of anatase type titanium oxide powder. Obtained. The amount of the vitamin B 12 derivative supported on the dehalogenation catalyst was 7.0 × 10 −11 mol / cm 2 per unit surface area of the rutile-type titanium oxide powder, and 54 mg / g per unit mass.
この脱ハロゲン化触媒は、Ｃｏ(III)を示す赤色を呈していた。この脱ハロゲン化触媒をエタノールと混合し、ブラックライト〔フナコシ(株)製、１５Ｗ〕により紫外光を１時間照射したところ、Ｃｏ(Ｉ)を示す緑色を呈した。 This dehalogenation catalyst had a red color indicating Co (III). When this dehalogenation catalyst was mixed with ethanol and irradiated with ultraviolet light with a black light (Funakoshi Co., Ltd., 15 W) for 1 hour, a green color indicating Co (I) was obtained.
〔有機ハロゲン化物の脱ハロゲン化〕
実施例１で得た脱ハロゲン化触媒に代えて上記で得た脱ハロゲン化触媒２０ｍｇを用い、実施例１で用いた有機ハロゲン化物に代えて第２表に示す有機ハロゲン化物を用いた以外は実施例１と同様に操作して照射して脱ハロゲン化を行い、転化率を求めた。結果を第２表に示す。
[Dehalogenation of organic halides]
20 mg of the above-obtained dehalogenation catalyst was used in place of the dehalogenation catalyst obtained in Example 1, and the organic halides shown in Table 2 were used in place of the organic halides used in Example 1. The dehalogenation was carried out by irradiation in the same manner as in Example 1 to obtain the conversion rate. The results are shown in Table 2.
第 ２ 表
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
試験 有機ハロゲン化物 転化率 番号 （％）
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
１ ブロモエチルベンゼン ３５
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Table 2
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Test Organic Halide Conversion Number (%)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
1 Bromoethylbenzene 35
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例３
〔脱ハロゲン化触媒の調製〕
アナターゼ型酸化チタン粉末に代えて、アナターゼ・ルチル型酸化チタン粉末〔日本エアロジル(株)製、「Ｐ−２５」〕０．１５ｇを用いた以外は実施例１と同様に操作して、脱ハロゲン化触媒を得た。この脱ハロゲン化触媒のビタミンＢ12誘導体の担持量は、ルチル型酸化チタン粉末の単位表面積あたりで７．０×１０-11モル／ｃｍ2であり、単位質量あたりで５２ｍｇ／ｇであった。
Example 3
(Preparation of dehalogenation catalyst)
Dehalogenation was carried out in the same manner as in Example 1 except that 0.15 g of anatase / rutile type titanium oxide powder (“P-25” manufactured by Nippon Aerosil Co., Ltd.) was used instead of anatase type titanium oxide powder. A catalyst was obtained. The amount of the vitamin B 12 derivative supported on this dehalogenation catalyst was 7.0 × 10 −11 mol / cm 2 per unit surface area of the rutile-type titanium oxide powder, and 52 mg / g per unit mass.
この脱ハロゲン化触媒は、Ｃｏ(III)を示す赤色を呈していた。この脱ハロゲン化触媒をエタノールと混合し、ブラックライト〔フナコシ(株)製、１５Ｗ〕により紫外光を１時間照射したところ、Ｃｏ(Ｉ)を示す緑色を呈した。 This dehalogenation catalyst had a red color indicating Co (III). When this dehalogenation catalyst was mixed with ethanol and irradiated with ultraviolet light with a black light (Funakoshi Co., Ltd., 15 W) for 1 hour, a green color indicating Co (I) was obtained.
〔有機ハロゲン化物の脱ハロゲン化〕
実施例１で得た脱ハロゲン化触媒に代えて上記で得た脱ハロゲン化触媒２０ｍｇを用い、実施例１で用いた有機ハロゲン化物に代えて第３表に示す有機ハロゲン化物を用いた以外は実施例１と同様に操作して照射して脱ハロゲン化を行い、転化率を求めた。結果を第３表に示す。
[Dehalogenation of organic halides]
20 mg of the above-obtained dehalogenation catalyst was used in place of the dehalogenation catalyst obtained in Example 1, and the organic halides shown in Table 3 were used in place of the organic halides used in Example 1. The dehalogenation was carried out by irradiation in the same manner as in Example 1 to obtain the conversion rate. The results are shown in Table 3.
第 ３ 表
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
試験 有機ハロゲン化物 転化率 番号 （％）
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
１ ２−ブロモエチルベンゼン ９５
２ １，１−ビス（４−クロロフェニル）−２，２，２−トリクロロエタン ９９
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Table 3
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Test Organic Halide Conversion Number (%)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
1 2-Bromoethylbenzene 95
2 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane 99
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例４
第４表に示す有機ハロゲン化物を３ミリモル／Ｌ（３ｍｍｏｌ／Ｌ）の濃度でエタノールに溶解させ、３０ｍＬを秤取り、石英ガラス製セルに入れた。次いで、実施例１で用いたビタミンＢ12誘導体（コビリン酸）０．７６ｍｇおよび実施例１で用いたアナターゼ型酸化チタン粉末〔ＳＴ−２１〕２０ｍｇを加え、撹拌して懸濁させながら窒素ガスをバブリングさせて溶存酸素を除去し、次いで攪拌下にブラックライト〔フナコシ(株)製、１５Ｗ〕により、反応セル外表面における紫外光強度１．７６ｍＷ／ｃｍ2で紫外光を２４時間照射して脱ハロゲン化を行った。照射後、実施例１と同様にして、転化率を求めた。結果を第４表に示す。
Example 4
The organic halides shown in Table 4 were dissolved in ethanol at a concentration of 3 mmol / L (3 mmol / L), 30 mL was weighed and placed in a quartz glass cell. Next, 0.76 mg of vitamin B 12 derivative (cobyrinic acid) used in Example 1 and 20 mg of anatase-type titanium oxide powder [ST-21] used in Example 1 were added, and nitrogen gas was added while stirring and suspending. Dissolved oxygen was removed by bubbling, and then de-irradiated with black light (Funakoshi Co., Ltd., 15 W) under stirring at a UV light intensity of 1.76 mW / cm 2 on the outer surface of the reaction cell for 24 hours. Halogenation was performed. After the irradiation, the conversion rate was determined in the same manner as in Example 1. The results are shown in Table 4.
第 ４ 表
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
試験 有機ハロゲン化物 転化率 番号 （％）
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
１ ２−ブロモエチルベンゼン ６０
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Table 4
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Test Organic Halide Conversion Number (%)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
1 2-Bromoethylbenzene 60
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
比較例１
第４表に示す有機ハロゲン化物に代えて第５表に示す有機ハロゲン化物を用い、アナターゼ型酸化チタン粉末〔ＳＴ−２１〕を用いなかった以外は実施例４と同様に操作して脱ハロゲン化を行い、転化率を求めた。結果を第５表に示す。
Comparative Example 1
Dehalogenation was carried out in the same manner as in Example 4 except that the organic halides shown in Table 5 were used instead of the organic halides shown in Table 4 and the anatase-type titanium oxide powder [ST-21] was not used. And the conversion was determined. The results are shown in Table 5.
第 ５ 表
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
試験 有機ハロゲン化物 転化率 番号 （％）
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
１ ２−ブロモエチルベンゼン ０
２ １，１−ビス（４−クロロフェニル）−２，２，２−トリクロロエタン ０
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Table 5
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Test Organic Halide Conversion Number (%)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
1 2-Bromoethylbenzene 0
2 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane 0
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
比較例２
第４表に示す有機ハロゲン化物に代えて第６表に示す有機ハロゲン化物を用い、ビタミンＢ12誘導体を用いなかった以外は実施例４と同様に操作して脱ハロゲン化を行い、転化率を求めた。結果を第６表に示す。
Comparative Example 2
In place of the organic halide shown in Table 4, the organic halide shown in Table 6 was used, and dehalogenation was carried out in the same manner as in Example 4 except that the vitamin B 12 derivative was not used. Asked. The results are shown in Table 6.
第 ６ 表
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
試験 有機ハロゲン化物 転化率 番号 （％）
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
１ ２−ブロモエチルベンゼン ０
２ １，１−ビス（４−クロロフェニル）−２，２，２−トリクロロエタン ０
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Table 6
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Test Organic Halide Conversion Number (%)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
1 2-Bromoethylbenzene 0
2 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane 0
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例５
〔脱ハロゲン化触媒の調製〕
アナターゼ型酸化チタン粉末〔ＳＴ−２１〕に代えて、可視光応答型酸化チタン光触媒粉末〔住友化学(株)製、「ＴＰ−Ｓ２０１」〕０．１５ｇを用いた以外は実施例１と同様に操作して、脱ハロゲン化触媒を得た。この脱ハロゲン化触媒のビタミンＢ12誘導体の担持量は、用いた光触媒粉末の単位表面積あたりで８．０×１０-11モル／ｃｍ2であり、単位質量あたりで３８ｍｇ／ｇであった。
Example 5
(Preparation of dehalogenation catalyst)
In place of anatase type titanium oxide powder [ST-21], a visible light responsive type titanium oxide photocatalyst powder (manufactured by Sumitomo Chemical Co., Ltd., “TP-S201”) was used in the same manner as in Example 1, except that 0.15 g was used. Operation yielded a dehalogenated catalyst. The amount of the vitamin B 12 derivative supported on this dehalogenation catalyst was 8.0 × 10 −11 mol / cm 2 per unit surface area of the photocatalyst powder used, and 38 mg / g per unit mass.
この脱ハロゲン化触媒は、Ｃｏ(III)を示す赤色を呈していた。この脱ハロゲン化触媒をエタノールと混合し、タングステンランプ〔ＰＨＩＬＩＰＳ社製、「Ｆｏｃｕｓ Ｌｉｎｅ」〕により可視光を２時間照射したところ、Ｃｏ(Ｉ)を示す緑色を呈した。なお、タングステンランプは紫外光を発しない。 This dehalogenation catalyst had a red color indicating Co (III). When this dehalogenation catalyst was mixed with ethanol and irradiated with visible light for 2 hours with a tungsten lamp ("Focus Line" manufactured by PHILIPS), a green color indicating Co (I) was obtained. The tungsten lamp does not emit ultraviolet light.
〔有機ハロゲン化物の脱ハロゲン化〕
有機ハロゲン化物をエタノールに溶解させ、石英ガラス製セルに入れる。次いで、上記で得た脱ハロゲン化触媒を浸漬し、撹拌しながら窒素ガスをバブリングさせて溶存酸素を除去し、次いで攪拌下に、可視光を照射することにより、有機ハロゲン化物を高い転化率で脱ハロゲン化することができる。
[Dehalogenation of organic halides]
The organic halide is dissolved in ethanol and placed in a quartz glass cell. Next, the dehalogenation catalyst obtained above is immersed, nitrogen gas is bubbled with stirring to remove dissolved oxygen, and then, under stirring, the organic halide is irradiated with visible light at a high conversion rate. It can be dehalogenated.
実施例６
〔脱ハロゲン化触媒の調製〕
光学顕微鏡観察に用いる無機ガラス製のプレパラートを十分に脱脂洗浄し、可視光応答型光触媒酸化チタン粉末の分散液〔住友化学(株)製、「ＴＳ−Ｓ４１１０」〕を塗布し、乾燥させて、プレパラートに可視光応答型光触媒酸化チタンの粉末を担持する。次いで実施例１で用いたと同じビタミンＢ12誘導体をエタノールに溶解させた溶液を塗布し、乾燥させて、プレパラート上に可視光応答型光触媒酸化チタンの粉末が担持され、この粉末にビタミンＢ12誘導体が担持された脱ハロゲン化触媒を得る。
Example 6
(Preparation of dehalogenation catalyst)
The inorganic glass preparation used for the optical microscope observation is thoroughly degreased and washed, and a dispersion of visible light responsive photocatalytic titanium oxide powder (manufactured by Sumitomo Chemical Co., Ltd., “TS-S4110”) is dried and dried. The preparation is loaded with a powder of visible light responsive photocatalytic titanium oxide. Next, a solution in which the same vitamin B 12 derivative used in Example 1 was dissolved in ethanol was applied and dried, and a visible light responsive photocatalytic titanium oxide powder was supported on the preparation, and the vitamin B 12 derivative was supported on this powder. To obtain a dehalogenated catalyst on which is supported.
〔有機ハロゲン化物の脱ハロゲン化〕
有機ハロゲン化物をエタノールに溶解させ、石英ガラス製セルに入れる。次いで、上記で得た脱ハロゲン化触媒を浸漬し、撹拌しながら窒素ガスをバブリングさせて溶存酸素を除去し、次いで攪拌下に、可視光を照射することにより、有機ハロゲン化物を高い転化率で脱ハロゲン化することができる。
[Dehalogenation of organic halides]
The organic halide is dissolved in ethanol and placed in a quartz glass cell. Next, the dehalogenation catalyst obtained above is immersed, nitrogen gas is bubbled with stirring to remove dissolved oxygen, and then, under stirring, the organic halide is irradiated with visible light at a high conversion rate. It can be dehalogenated.
実施例７
実施例１で用いたビタミンＢ12誘導体（コビリン酸）に代えて、ビタミンＢ12（シアノコバラミン）１３ｍｇを用いた以外は実施例１と同様に操作して、脱ハロゲン化触媒を得た。この脱ハロゲン化触媒は、Ｃｏ(III)を示す赤色を呈していた。この脱ハロゲン化触媒をエタノールと混合し、ブラックライト〔フナコシ(株)製、１５Ｗ〕により紫外光を１時間照射したところ、Ｃｏ(Ｉ)を示す緑色を呈した。
Example 7
A dehalogenation catalyst was obtained in the same manner as in Example 1 except that 13 mg of vitamin B 12 (cyanocobalamin) was used instead of the vitamin B 12 derivative (cobilic acid) used in Example 1. This dehalogenation catalyst had a red color indicating Co (III). When this dehalogenation catalyst was mixed with ethanol and irradiated with ultraviolet light with a black light (Funakoshi Co., Ltd., 15 W) for 1 hour, a green color indicating Co (I) was obtained.
実施例１で得た脱ハロゲン化触媒に代えて上記で得た脱ハロゲン化触媒を用いる以外は実施例１と同様に操作することにより、有機ハロゲン化物を脱ハロゲン化することができる。 The organic halide can be dehalogenated by the same operation as in Example 1 except that the dehalogenation catalyst obtained above is used instead of the dehalogenation catalyst obtained in Example 1.
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