JP3757275B2 - Process for producing dialkylformamide from carbon dioxide - Google Patents
Process for producing dialkylformamide from carbon dioxide Download PDFInfo
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- JP3757275B2 JP3757275B2 JP2002226773A JP2002226773A JP3757275B2 JP 3757275 B2 JP3757275 B2 JP 3757275B2 JP 2002226773 A JP2002226773 A JP 2002226773A JP 2002226773 A JP2002226773 A JP 2002226773A JP 3757275 B2 JP3757275 B2 JP 3757275B2
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- carbon dioxide
- dialkylformamide
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Description
【０００１】
【発明の属する技術分野】
本発明は、二酸化炭素を原料とし、これから光エネルギーと金属錯体触媒を用いてジアルキルホルムアミドを製造する方法に関する。
【０００２】
【従来の技術】
レニウムやルテニウム等の金属錯体は、電子供与剤（アミン等）の存在下で紫外―可視領域の光を照射することによって二酸化炭素を還元する光触媒能を有することが知られている。しかし、この場合、生成物としては、付加価値の低い一酸化炭素しか得られない。
【０００３】
【発明が解決しようとする課題】
本発明は、金属錯体を用いる二酸化炭素の光還元反応において、一酸化炭素以外の有用な化学物質を製造する方法を提供することをその課題とする。
【０００４】
【課題を解決するための手段】
この出願によれば、以下の発明が提供される。
（１）二酸化炭素からのジアルキルホルムアミドの製造方法であって、二酸化炭素、該二酸化炭素を一酸化炭素に光還元する性能を有する金属錯体及びジアルキルアミンを含む共存系に、光照射することを特徴とする二酸化炭素からのジアルキルホルムアミドの製造方法
（２）反応温度を８０〜１００℃とすることを特徴とする上記（１）に記載のジアルキルホルムアミドの製造方法
（３）溶媒として１−メチル−２−ピロリドンを用いることを特徴とする上記（１）または（２）に記載のジアルキルホルムアミドの製造方法
【０００５】
【発明の実施の形態】
本発明で用いる金属錯体は、二酸化炭素を電子供与剤（アミン等）の存在下で光還元する性能を有するものである。このようなものは、従来公知のものである。
【０００６】
この金属錯体において、その金属成分は、その錯体が電子供与剤の存在下で二酸化炭素を一酸化炭素に光還元し得るものであればよく、特に制約されないが、通常は、周期律表第８族金属の中から選ばれる。このような金属の具体例としては、例えば、レニウム、ルテニウム、オスミウム、ニッケル、コバルト等が挙げられる。
【０００７】
また、前記金属錯体において、その金属成分に対する配位子としては、該金属成分に配位し、錯体を形成する配位子が用いられる。この場合の典型的な配位子としては、含窒素複素環化合物や含酸素複素環化合物、含イオウ複素環化合物等があげられる。これらの配位子の分子量は、通常、５０〜１０００、好ましくは７０〜５００である。
【０００８】
本発明で用いる金属錯体は、その配位子−金属間の電荷移動吸収バンドを紫外部から可視部にかけて有するものである。
【０００９】
本発明の反応において、その反応温度は３０〜１５０℃、好ましくは８０〜１００℃である。二酸化炭素の圧力は２〜６ＭＰａ付近が最適であり、あまり高圧にして二酸化炭素が液体もしくは超臨界状態になってしまうとかえって生成物の収量は抑制される。
【００１０】
本発明で用いるジアルキルアミンは、そのアルキル基の炭素数が１〜８、好ましくは１〜６のものである。このようなものとしては、例えば、ジメチルアミン、ジエチルアミン、ジイソプロピルアミンなどが挙げられる。
【００１１】
本発明の反応は、有機溶媒を用いて実施することができるが、この場合の有機溶媒としては、１−メチル−２−ピロリドン等の熱にも安定でそれ自身はジアルキルアミンとも反応せずしかも金属錯体やアミンを十分溶解できる極性溶媒やイオン性流体が適している。
【００１２】
光照射条件は特に制約されないが、照射する光の波長は、金属錯体の配位子−金属間の電荷移動吸収バンド領域にしておくことが望ましく、通常、２００〜８００ｎｍ、好ましくは２５０〜５００ｎｍである。光源の種類は特に制約されず、水銀灯、キセノンランプ、太陽光等を光の波長に応じて適宜使用すれば良い。光照射時間も特に制約されず、５〜５０時間程度で十分である。
【００１３】
【実施例】
次に本発明を実施例によりさらに詳細に説明する。
【００１４】
実施例１
レニウム錯体［Ｒｅ（２，２’−ｂｉｐｙｒｉｄｉｎｅ）（ＣＯ）３Ｃｌ（２．２×１０−７モル）をサファイア窓付きステンレス製高圧反応容器（内容量１７ｍＬ）にいれ、９ｍＬの１−メチル−２−ピロリドン、１ｍＬのトリエチルアミンを入れた。さらに０．２ｍＬのジエチルアミンを入れた後、二酸化炭素を３．８ｇ導入した。反応容器を１００℃に加熱後、サファイア窓を介して３６５ｎｍの近紫外光を０−１８時間照射した。照射後室温まで冷却し、サンプリングバッグを接続し常圧にもどしてガスを回収し、ガスクロマトグラフィーでガス層中の生成物を分析した。一方、有機溶媒層中の生成物もガスクロマト質量分析計で分析した。その結果、１６時間照射で６．１μｍｏｌの一酸化炭素、６．５μｍｏｌのジエチルホルムアミドが得られた。
【００１５】
次に、前記反応において、一酸化炭素及びジエチルホルムアミドの生成量と反応時間（照射時間）との関係を示す。
【００１６】
比較例１
実施例１において、レニウム錯体を導入せずに反応を行った。この場合には、ジエチルホルムアミドの生成は観測されなかった。
【００１７】
【発明の効果】
以上のように、金属錯体を用いる二酸化炭素の光還元反応において、ジアルキルアミンを反応系に添加することでジアルキルホルムアミドを得ることができた。
【図面の簡単な説明】
【図１】実施例１の場合の一酸化炭素およびジエチルホルムアミド生成量と反応時間との関係を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing a dialkylformamide from carbon dioxide as a raw material and using light energy and a metal complex catalyst.
[0002]
[Prior art]
It is known that metal complexes such as rhenium and ruthenium have a photocatalytic ability to reduce carbon dioxide by irradiating light in the ultraviolet-visible region in the presence of an electron donor (such as amine). However, in this case, only a carbon monoxide having a low added value can be obtained as a product.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a useful chemical substance other than carbon monoxide in a photoreduction reaction of carbon dioxide using a metal complex.
[0004]
[Means for Solving the Problems]
According to this application, the following invention is provided.
(1) A method for producing a dialkylformamide from carbon dioxide, characterized by irradiating light to a coexisting system containing carbon dioxide, a metal complex having a performance of photoreducing the carbon dioxide to carbon monoxide, and a dialkylamine. (2) The method for producing a dialkylformamide according to (1) above, wherein the reaction temperature is 80 to 100 ° C. (3) 1-methyl-2 as a solvent A process for producing a dialkylformamide as described in (1) or (2) above, wherein pyrrolidone is used
DETAILED DESCRIPTION OF THE INVENTION
The metal complex used in the present invention is capable of photoreducing carbon dioxide in the presence of an electron donor (such as an amine). Such a thing is a conventionally well-known thing.
[0006]
In this metal complex, the metal component is not particularly limited as long as the complex can photoreduct carbon dioxide to carbon monoxide in the presence of an electron donor. Selected from group metals. Specific examples of such metals include rhenium, ruthenium, osmium, nickel, cobalt, and the like.
[0007]
In the metal complex, as a ligand for the metal component, a ligand that coordinates to the metal component to form a complex is used. Typical ligands in this case include nitrogen-containing heterocyclic compounds, oxygen-containing heterocyclic compounds, sulfur-containing heterocyclic compounds and the like. The molecular weight of these ligands is usually 50 to 1000, preferably 70 to 500.
[0008]
The metal complex used in the present invention has a charge transfer absorption band between its ligand and metal from the ultraviolet part to the visible part.
[0009]
In the reaction of the present invention, the reaction temperature is 30 to 150 ° C, preferably 80 to 100 ° C. The pressure of carbon dioxide is optimal in the vicinity of 2 to 6 MPa. If the pressure is too high and the carbon dioxide becomes liquid or supercritical, the yield of the product is suppressed.
[0010]
The dialkylamine used in the present invention has 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms in the alkyl group. Examples of such include dimethylamine, diethylamine, and diisopropylamine.
[0011]
The reaction of the present invention can be carried out using an organic solvent. In this case, the organic solvent is stable to heat such as 1-methyl-2-pyrrolidone and itself does not react with dialkylamine. Polar solvents and ionic fluids that can sufficiently dissolve metal complexes and amines are suitable.
[0012]
The light irradiation conditions are not particularly limited, but the wavelength of the light to be irradiated is desirably a charge transfer absorption band region between the ligand and the metal of the metal complex, and is usually 200 to 800 nm, preferably 250 to 500 nm. is there. The type of the light source is not particularly limited, and a mercury lamp, a xenon lamp, sunlight, or the like may be appropriately used according to the wavelength of light. The light irradiation time is not particularly limited, and about 5 to 50 hours is sufficient.
[0013]
【Example】
Next, the present invention will be described in more detail with reference to examples.
[0014]
Example 1
The rhenium complex [Re (2,2′-bipyridine) (CO) 3 Cl (2.2 × 10 −7 mol) is placed in a stainless steel high-pressure reaction vessel (content 17 mL) with a sapphire window, and 9 mL of 1-methyl- 2-Pyrrolidone, 1 mL of triethylamine was added. After adding 0.2 mL of diethylamine, 3.8 g of carbon dioxide was introduced. The reaction vessel was heated to 100 ° C. and irradiated with near-ultraviolet light of 365 nm through a sapphire window for 0-18 hours. After irradiation, the sample was cooled to room temperature, a sampling bag was connected, the pressure was returned to normal pressure, the gas was recovered, and the product in the gas layer was analyzed by gas chromatography. On the other hand, the product in the organic solvent layer was also analyzed with a gas chromatograph mass spectrometer. As a result, 6.1 μmol of carbon monoxide and 6.5 μmol of diethylformamide were obtained after irradiation for 16 hours.
[0015]
Next, in the above reaction, the relationship between the amount of carbon monoxide and diethylformamide produced and the reaction time (irradiation time) is shown.
[0016]
Comparative Example 1
In Example 1, the reaction was carried out without introducing the rhenium complex. In this case, formation of diethylformamide was not observed.
[0017]
【The invention's effect】
As described above, in the photoreduction reaction of carbon dioxide using a metal complex, dialkylformamide could be obtained by adding dialkylamine to the reaction system.
[Brief description of the drawings]
1 is a graph showing the relationship between the amount of carbon monoxide and diethylformamide produced and the reaction time in Example 1. FIG.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002226773A JP3757275B2 (en) | 2002-08-05 | 2002-08-05 | Process for producing dialkylformamide from carbon dioxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002226773A JP3757275B2 (en) | 2002-08-05 | 2002-08-05 | Process for producing dialkylformamide from carbon dioxide |
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| Publication Number | Publication Date |
|---|---|
| JP2004067550A JP2004067550A (en) | 2004-03-04 |
| JP3757275B2 true JP3757275B2 (en) | 2006-03-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002226773A Expired - Lifetime JP3757275B2 (en) | 2002-08-05 | 2002-08-05 | Process for producing dialkylformamide from carbon dioxide |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5522343B2 (en) * | 2009-02-12 | 2014-06-18 | スタンレー電気株式会社 | Carbon dioxide reduction equipment |
| JP5532776B2 (en) * | 2009-09-10 | 2014-06-25 | 株式会社豊田中央研究所 | Photocatalyst and method for producing photocatalyst |
| CN103214387A (en) * | 2013-05-03 | 2013-07-24 | 山东华鲁恒升化工股份有限公司 | Method for preparing N,N-diethylformamide |
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