JP3343585B2 - Hydroformylation method using carbon dioxide - Google Patents
Hydroformylation method using carbon dioxideInfo
- Publication number
- JP3343585B2 JP3343585B2 JP2000046494A JP2000046494A JP3343585B2 JP 3343585 B2 JP3343585 B2 JP 3343585B2 JP 2000046494 A JP2000046494 A JP 2000046494A JP 2000046494 A JP2000046494 A JP 2000046494A JP 3343585 B2 JP3343585 B2 JP 3343585B2
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated bond
- organic compound
- carbon dioxide
- hydroformylating
- yield
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【発明の属する産業分野】本発明は二酸化炭素を用い
て、不飽和結合を持つ有機化合物をヒドロホルミル化
し、アルデヒドまたはアルコールを製造する方法に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an aldehyde or an alcohol by hydroformylating an organic compound having an unsaturated bond using carbon dioxide.
【０００２】[0002]
【従来技術】ヒドロホルミル化法は不飽和結合を持つ有
機化合物を一酸化炭素および水素で処理することにより
アルデヒドまたはアルコールを製造する技術である。こ
の技術はすでに６０年以上もの歴史を持ち、国内外では
主にコバルトやロジウムの金属錯体を触媒とする幾つも
のプラントが開発され、近年では４００万ｔ強もの化成
品がこれらの方法により製造されている（触媒講座第７
巻、触媒学会編、講談社（１９８５））。しかし、従来
法では毒性の極めて高い一酸化炭素を原料として用いな
ければならないという問題がある。一方、二酸化炭素は
地球温暖化の主要原因物質であるばかりでなく、ほとん
どの化学プロセスにおいて容易に入手可能な炭素資源で
もあり、その有効利用は資源循環の観点から将来重要な
技術となることが期待される。また、一酸化炭素に比べ
て毒性が極めて低く、炭素源として取り扱いやすいとい
う利点も有する。しかしながら、二酸化炭素は一酸化炭
素に比べて化学的に不活性であり、ヒドロホルミル化法
において原料として一酸化炭素の代わりに二酸化炭素を
原料とする技術はこれまでに報告されていない。2. Description of the Related Art The hydroformylation method is a technique for producing an aldehyde or an alcohol by treating an organic compound having an unsaturated bond with carbon monoxide and hydrogen. This technology has a history of more than 60 years, and a number of plants have been developed in Japan and overseas, mainly using metal complexes of cobalt and rhodium as catalysts. In recent years, over 4 million tons of chemical products have been manufactured by these methods. Yes (catalyst course 7
Vol., Edited by the Catalysis Society of Japan, Kodansha (1985)). However, the conventional method has a problem that extremely toxic carbon monoxide must be used as a raw material. On the other hand, carbon dioxide is not only a major cause of global warming but also a readily available carbon resource in most chemical processes, and its effective use may become an important technology in the future from the viewpoint of resource recycling. Be expected. Further, it has an advantage that it has extremely low toxicity compared to carbon monoxide and is easy to handle as a carbon source. However, carbon dioxide is chemically inert as compared with carbon monoxide, and a technique using carbon dioxide as a raw material instead of carbon monoxide as a raw material in a hydroformylation method has not been reported so far.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、従来行われ
てきたヒドロホルミル化法において、一酸化炭素の代わ
りに二酸化炭素を原料として用いる新しい手法を提供す
る。SUMMARY OF THE INVENTION The present invention provides a new method of using carbon dioxide as a raw material instead of carbon monoxide in a conventionally performed hydroformylation method.
【０００４】[0004]
【課題を解決するための手段】本発明者は、上記のよう
な技術の現状に鑑みて、不飽和結合を持つ有機化合物と
二酸化炭素と水素を反応させる研究を進めた結果、有機
溶媒に均一に溶解するルテニウム化合物を触媒として用
いると、不飽和結合を持つ有機化合物をヒドロホルミル
化できることを見出したものである。さらに、より好ま
しくは、ハロゲン化物塩を併用した触媒系を用いること
により、さらに効率良く、その目的を達成し得ることを
見いだした。すなわち、本発明で用いる原料ガスは、水
素と二酸化炭素を主成分とする混合ガスである。二酸化
炭素の含有量は１０〜９０ｖｏｌ％、好ましくは５０〜
８０ｖｏｌ％、水素の含有量は１０〜９０ｖｏｌ％、好
ましくは２０〜５０ｖｏｌ％である。これらは混合ガス
の形で供給してもよく、また別々に供給してもよい。原
料ガス中に一酸化炭素が混入している必要は全くない
が、混入していたとしても差し支えない。原料として用
いる不飽和結合を持つ有機化合物としては、二重結合あ
るいは三重結合を持つ有機化合物を目的に応じて任意に
選択することができる。具体的には、エチレン、プロピ
レン、ブテン、イソブテン、アセチレン、スチレン、シ
クロヘキセン等がある。Means for Solving the Problems In view of the above-mentioned state of the art, the present inventor has conducted research on reacting an organic compound having an unsaturated bond with carbon dioxide and hydrogen. It has been found that an organic compound having an unsaturated bond can be hydroformylated by using a ruthenium compound soluble in water as a catalyst. Furthermore, more preferably, it has been found that the object can be achieved more efficiently by using a catalyst system in combination with a halide salt. That is, the source gas used in the present invention is a mixed gas containing hydrogen and carbon dioxide as main components. The content of carbon dioxide is 10 to 90 vol%, preferably 50 to 90 vol%.
The content of hydrogen is 80 to 90% by volume, preferably 20 to 50% by volume. These may be supplied in the form of a mixed gas or may be supplied separately. It is not absolutely necessary that carbon monoxide be mixed in the raw material gas, but it can be. As the organic compound having an unsaturated bond used as a raw material, an organic compound having a double bond or a triple bond can be arbitrarily selected according to the purpose. Specifically, there are ethylene, propylene, butene, isobutene, acetylene, styrene, cyclohexene and the like.
【０００５】[0005]
【本発明の実施の形態】本発明の触媒系は、有機溶媒に
溶解可能なあらゆるルテニウム化合物を含有する。より
好ましくは、Ｒｕ3（ＣＯ）12、Ｈ4Ｒｕ4（ＣＯ）12、
Ｈ2Ｒｕ6（ＣＯ）18等のクラスター化したルテニウム化
合物が適している。また、これらのクラスター化合物の
原料になる単核のルテニウム化合物を反応前あるいは反
応中にクラスター化処理して用いることもできる。触媒
使用量は反応液に対し約０．５〜１ｗｔ程度が好まし
い。触媒系はさらにハロゲン化物塩を含むことが望まし
い。ハロゲン化物イオンを供給する塩であれば特に限定
されない。ハロゲン化物としては特に塩化物が好まし
く、またカチオンとしてはアルカリ金属並びに第４級ホ
スホニウム、第４級アンモニウムが好ましい。具体的な
例としては、塩化リチウム、塩化ナトリウム、塩化カリ
ウム、［（Ｐｈ3Ｐ）2Ｎ］Ｃｌ、［（Ｃ2Ｈ5）4Ｎ］Ｃ
ｌ等がある。添加量は触媒量に対して１〜１０当量程度
が好ましい。本発明の方法は、好ましくは、非プロトン
性の有機溶媒中で行われる。それは、ルテニウム化合物
並びにハロゲン化物塩を少なくとも部分的に溶解させる
ことのできるものでなければならない。適当な溶媒とし
ては、芳香族炭化水素、エーテル、アミド、スルホニル
化合物などと、これらの混合物がある。特定の例は、テ
トラヒドロフラン、Ｎ−メチル−２−ピロリドン、スル
ホランである。本発明の方法は一般的に触媒系を含む有
機溶媒中に不飽和結合を持つ有機化合物を加え、二酸化
炭素並びに水素を加圧供給することによって行われる。
この方法は約１００℃〜１８０℃の範囲で行うことが好
ましい。より好ましい範囲は１２０℃〜１６０℃であ
る。これより低い温度域では二酸化炭素は反応せず、こ
れより高い温度域では不飽和結合の水素化のみが優先し
て起こる。圧力は１〜２０ＭＰａ、好ましくは２〜１０
ＭＰａである。DETAILED DESCRIPTION OF THE INVENTION The catalyst system of the present invention contains any ruthenium compound that is soluble in an organic solvent. More preferably, Ru 3 (CO) 12 , H 4 Ru 4 (CO) 12 ,
Clustered ruthenium compounds such as H 2 Ru 6 (CO) 18 are suitable. Further, a mononuclear ruthenium compound serving as a raw material of these cluster compounds can be used after being subjected to a clustering treatment before or during the reaction. The amount of the catalyst used is preferably about 0.5 to 1 wt. Desirably, the catalyst system further comprises a halide salt. The salt is not particularly limited as long as it supplies a halide ion. As the halide, chloride is particularly preferable, and as the cation, alkali metal and quaternary phosphonium and quaternary ammonium are preferable. As specific examples, lithium chloride, sodium chloride, potassium chloride, [(Ph 3 P) 2 N] Cl, [(C 2 H 5 ) 4 N] C
l. The addition amount is preferably about 1 to 10 equivalents to the catalyst amount. The method of the present invention is preferably performed in an aprotic organic solvent. It must be able to at least partially dissolve the ruthenium compound as well as the halide salt. Suitable solvents include aromatic hydrocarbons, ethers, amides, sulfonyl compounds, and the like, and mixtures thereof. Particular examples are tetrahydrofuran, N-methyl-2-pyrrolidone, sulfolane. The method of the present invention is generally carried out by adding an organic compound having an unsaturated bond to an organic solvent containing a catalyst system, and supplying carbon dioxide and hydrogen under pressure.
This method is preferably performed at a temperature in the range of about 100C to 180C. A more preferred range is from 120C to 160C. In the lower temperature range, the carbon dioxide does not react, and in the higher temperature range, only the hydrogenation of the unsaturated bond occurs preferentially. Pressure is 1 to 20 MPa, preferably 2 to 10 MPa
MPa.
【０００６】本発明の実施の形態は次の通りである。 （１） 不飽和結合を持つ有機化合物と二酸化炭素と水
素を、ルテニウム化合物を触媒として用いて、温度１０
０℃〜１８０℃、圧力１〜２０ＭＰａで、当該不飽和結
合を持つ有機化合物をヒドロホルミル化する方法。 （２） ルテニウム化合物が、クラスター化したルテニ
ウム錯体である上記１に記載された不飽和結合を持つ有
機化合物をヒドロホルミル化する方法。 （３） ルテニウム化合物が、Ｒｕ３（ＣＯ）１２、Ｈ
４Ｒｕ４（ＣＯ）１２、Ｈ２Ｒｕ６（ＣＯ）１８の１又
は２以上である上記１又は上記２に記載された不飽和結
合を持つ有機化合物をヒドロホルミル化する方法。 （４） さらに、ハロゲン化物塩を併用することにを特
徴とする上記１〜上記３のいずれかひとつに記載された
不飽和結合を持つ有機化合物をヒドロホルミル化する方
法。 （５） 不飽和結合を持つ有機化合物がオレフィン又は
アセチレンである上記１〜上記４のいずれかひとつに記
載された不飽和結合を持つ有機化合物をヒドロホルミル
化する方法。 （６） 温度１２０℃〜１６０℃、圧力２〜１０ＭＰａ
で行う上記１〜上記５のいずれかひとつに記載された不
飽和結合を持つ有機化合物をヒドロホルミル化する方
法。An embodiment of the present invention is as follows. (1) Using an organic compound having an unsaturated bond, carbon dioxide and hydrogen at a temperature of 10 using a ruthenium compound as a catalyst.
A method of hydroformylating an organic compound having an unsaturated bond at 0 ° C to 180 ° C and a pressure of 1 to 20 MPa. (2) The method for hydroformylating an organic compound having an unsaturated bond as described in (1) above, wherein the ruthenium compound is a clustered ruthenium complex. (3) The ruthenium compound is Ru 3 (CO) 12 , H
4. A method for hydroformylating an organic compound having an unsaturated bond as described in 1 or 2 above, which is 1 or 2 or more of 4 Ru 4 (CO) 12 and H 2 Ru 6 (CO) 18 . (4) The method for hydroformylating an organic compound having an unsaturated bond as described in any one of (1) to (3) above, further comprising using a halide salt in combination. (5) The method for hydroformylating an organic compound having an unsaturated bond according to any one of the above (1) to (4), wherein the organic compound having an unsaturated bond is an olefin or acetylene. (6) Temperature 120 ° C to 160 ° C, pressure 2 to 10 MPa
The method for hydroformylating an organic compound having an unsaturated bond according to any one of the above 1 to 5, which is carried out in the step.
【０００７】[0007]
【実施例】次の実施例は、本発明を例証するが、その範
囲を限定するものではない。 実施例１（３核クラスター錯体による反応） 内容積５０ｍｌのステンレス製加圧反応装置に室温でＲ
ｕ3（ＣＯ）12を０．１ｍｍｏｌ、［（Ｐｈ3Ｐ）2Ｎ］
Ｃｌを０．２ｍｍｏｌ、Ｎ−メチル−２−ピロリドンを
８．０ｍｌ、α−メチルスチレンを５．０ｍｍｏｌを入
れ、撹拌して溶解させたのち、二酸化炭素を４ＭＰａ、
水素を４０ＭＰａを撹拌しつつ圧入し、１３０℃で３０
時間保持した。その後反応装置を室温まで冷却し、放圧
して残存有機相を抜き取り、ガスクロマトグラフにて分
析した。α−メチルスチレンの転換率は９６％、ヒドロ
ホルミル化生成物として３−フェニル−１−ブタノール
が収率４１％、３−フェニル−１−ブタナールが収率１
３％生成し、水素化生成物としてクメンが収率３４％生
成した。The following examples illustrate the invention but do not limit its scope. Example 1 (Reaction with trinuclear cluster complex) R was added at room temperature to a stainless steel pressurized reactor having an inner volume of 50 ml.
u3 (CO) 12 to 0.1mmol, [(Ph 3 P) 2 N]
After 0.2 mmol of Cl, 8.0 ml of N-methyl-2-pyrrolidone and 5.0 mmol of α-methylstyrene were added and dissolved by stirring, carbon dioxide was dissolved at 4 MPa,
Inject hydrogen while stirring at 40 MPa, and at 130 ° C for 30
Hold for hours. Thereafter, the reactor was cooled to room temperature, and the pressure was released to remove the remaining organic phase, which was analyzed by gas chromatography. The conversion of α-methylstyrene is 96%, the yield of 3-phenyl-1-butanol is 41%, and the yield of 3-phenyl-1-butanal is 1 as the hydroformylation product.
3% and cumene was produced as a hydrogenated product in a yield of 34%.
【０００８】実施例２（４核クラスター錯体による反
応） Ｈ4Ｒｕ4（ＣＯ）12を０．１ｍｍｏｌ、ＬｉＣｌを０．
４ｍｍｏｌ、Ｎ−メチル−２−ピロリドンを８．０ｍ
ｌ、α−メチルスチレンを５．０ｍｍｏｌを用い、実施
例１と同条件で反応、分析した。α−メチルスチレンの
転換率は９８％、ヒドロホルミル化生成物として３−フ
ェニル−１−ブタノールが収率５２％、３−フェニル−
１−ブタナールが収率１０％生成し、水素化生成物とし
てクメンが収率２８％生成した。Example 2 (Reaction with tetranuclear cluster complex) 0.1 mmol of H 4 Ru 4 (CO) 12 and 0.1 mmol of LiCl.
4 mmol, 8.0 m of N-methyl-2-pyrrolidone
l, α-Methylstyrene was reacted and analyzed under the same conditions as in Example 1 using 5.0 mmol. The conversion of α-methylstyrene is 98%, the yield of 3-phenyl-1-butanol as hydroformylation product is 52%,
1-butanal was produced at a yield of 10%, and cumene was produced as a hydrogenated product at a yield of 28%.
【０００９】実施例３（単核錯体による反応） Ｃｓ［Ｒｕ（ＣＯ）3Ｃｌ3］を０．１ｍｍｏｌ、［（Ｐ
ｈ3Ｐ）2Ｎ］Ｃｌを０．２ｍｍｏｌ、Ｎ−メチル−２−
ピロリドンを８．０ｍｌ、α−メチルスチレンを５．０
ｍｍｏｌを用い、実施例１と同条件で反応、分析した。
α−メチルスチレンの転換率は６１％、ヒドロホルミル
化生成物として３−フェニル−１−ブタノールが収率１
５％、３−フェニル−１−ブタナールが収率２１％生成
し、水素化生成物としてクメンが収率２５％生成した。Example 3 (Reaction with Mononuclear Complex) 0.1 mmol of Cs [Ru (CO) 3 Cl 3 ] and [(P
h 3 P) 2 N] a Cl 0.2 mmol, N-methyl-2-
8.0 ml of pyrrolidone and 5.0 ml of α-methylstyrene.
Using mmol, the reaction was carried out and analyzed under the same conditions as in Example 1.
The conversion of α-methylstyrene was 61%, and 3-phenyl-1-butanol was obtained as a hydroformylation product at a yield of 1%.
5%, 3-phenyl-1-butanal was produced in a yield of 21%, and cumene was produced as a hydrogenated product in a yield of 25%.
【００１０】実施例４（塩無添加の例） ［（Ｐｈ3Ｐ）2Ｎ］［Ｒｕ（ＣＯ）3Ｃｌ3］を０．１ｍ
ｍｏｌ、Ｎ−メチル−２−ピロリドンを８．０ｍｌ、α
−メチルスチレンを５．０ｍｍｏｌを用い、実施例１と
同条件で反応、分析した。α−メチルスチレンの転換率
は８７％、ヒドロホルミル化生成物として３−フェニル
−１−ブタノールが収率２３％、３−フェニル−１−ブ
タナールが収率１２％生成し、水素化生成物としてクメ
ンが収率３５％生成した。Example 4 (Example without salt) [(Ph 3 P) 2 N] [Ru (CO) 3 Cl 3 ] was 0.1 m
mol, 8.0 ml of N-methyl-2-pyrrolidone, α
Using 5.0 mmol of -methylstyrene, the reaction was performed and analyzed under the same conditions as in Example 1. The conversion of α-methylstyrene is 87%, 3-phenyl-1-butanol is produced as a hydroformylation product in a yield of 23%, 3-phenyl-1-butanal is produced in a yield of 12%, and cumene is produced as a hydrogenation product. Was produced in a yield of 35%.
【００１１】実施例５（他のオレフィン化合物の例） Ｈ4Ｒｕ4（ＣＯ）12を０．１ｍｍｏｌ、ＬｉＣｌを０．
４ｍｍｏｌ、Ｎ−メチル−２−ピロリドンを８．０ｍ
ｌ、シクロヘキセンを５．０ｍｍｏｌを用い、実施例１
と同条件で反応、分析した。シクロヘキセンの転換率は
１００％、ヒドロホルミル化生成物としてヒドロキシメ
チルシクロヘキサンが収率７６％、ホルミルシクロヘキ
サンが収率１２％生成し、水素化生成物としてシクロヘ
キサンが収率８％生成した。Example 5 (Examples of other olefin compounds) 0.1 mmol of H 4 Ru 4 (CO) 12 and 0.1 mmol of LiCl.
4 mmol, 8.0 m of N-methyl-2-pyrrolidone
l, using 5.0 mmol of cyclohexene, Example 1
Reaction and analysis were performed under the same conditions as described above. The conversion of cyclohexene was 100%, the yield of hydroxymethylcyclohexane was 76%, the yield of formylcyclohexane was 12% as a hydroformylation product, and the yield of cyclohexane was 8% as a hydrogenation product.
【００１２】[0012]
【発明の効果】従来法によるヒドロホルミル化では、毒
性の極めて高い一酸化炭素を原料として用いなければな
らなかったが、本発明は、安全な二酸化炭素を用いても
行えることを確認した。ヒドロホルミル化反応に二酸化
炭素を用いることにより、二酸化炭素を有効利用するこ
とができるばかりか、地球温暖化を防ぐ一助ともなる。According to the hydroformylation by the conventional method, extremely toxic carbon monoxide had to be used as a raw material. However, it was confirmed that the present invention can be carried out using safe carbon dioxide. By using carbon dioxide for the hydroformylation reaction, not only carbon dioxide can be effectively used, but also it helps to prevent global warming.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０７Ｃ 33/05 Ｃ０７Ｃ 33/05 Ａ 33/18 33/18 45/00 45/00 47/228 47/228 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (58)調査した分野(Int.Cl.7，ＤＢ名) C07B 41/06 C07B 41/20 C07C 27/00 C07C 29/44 C07C 33/05 C07C 33/18 C07C 45/00 C07C 47/228 B01J 31/30 C07B 61/00 300 ＣＡＳＲＥＡＣＴ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI C07C 33/05 C07C 33/05 A 33/18 33/18 45/00 45/00 47/228 47/228 // C07B 61 / 00 300 C07B 61/00 300 (58) Fields investigated (Int. Cl. 7 , DB name) C07B 41/06 C07B 41/20 C07C 27/00 C07C 29/44 C07C 33/05 C07C 33/18 C07C 45 / 00 C07C 47/228 B01J 31/30 C07B 61/00 300 CASREACT (STN)
Claims (6)
素と水素を、ルテニウム化合物を触媒として用いて、温
度１００℃〜１８０℃、圧力１〜２０ＭＰａで、当該不
飽和結合を持つ有機化合物をヒドロホルミル化する方
法。An organic compound having an unsaturated bond is hydroformyl-containing an organic compound having an unsaturated bond, carbon dioxide and hydrogen at a temperature of 100 ° C. to 180 ° C. and a pressure of 1 to 20 MPa using a ruthenium compound as a catalyst. How to
ルテニウム錯体である請求項１に記載された不飽和結合
を持つ有機化合物をヒドロホルミル化する方法。2. The method for hydroformylating an organic compound having an unsaturated bond according to claim 1, wherein the ruthenium compound is a clustered ruthenium complex.
１２、Ｈ４Ｒｕ４（ＣＯ）１２、Ｈ２Ｒｕ６（ＣＯ）
１８の１又は２以上である請求項１又は請求項２に記載
された不飽和結合を持つ有機化合物をヒドロホルミル化
する方法。3. The method according to claim 1, wherein the ruthenium compound is Ru 3 (CO)
12 , H 4 Ru 4 (CO) 12 , H 2 Ru 6 (CO)
The method for hydroformylating an organic compound having an unsaturated bond according to claim 1 or 2, which is one or more of the compounds described in ( 18 ).
にを特徴とする請求項１〜請求項３のいずれかひとつに
記載された不飽和結合を持つ有機化合物をヒドロホルミ
ル化する方法。4. The method for hydroformylating an organic compound having an unsaturated bond according to any one of claims 1 to 3, further comprising using a halide salt in combination.
ン又はアセチレンである請求項１〜請求項４のいずれか
ひとつに記載された不飽和結合を持つ有機化合物をヒド
ロホルミル化する方法。5. The method for hydroformylating an organic compound having an unsaturated bond according to any one of claims 1 to 4, wherein the organic compound having an unsaturated bond is olefin or acetylene.
ＭＰａで行う請求項１〜請求項５のいずれかひとつに記
載された不飽和結合を持つ有機化合物をヒドロホルミル
化する方法。6. A temperature of 120 ° C. to 160 ° C. and a pressure of 2 to 10.
The method for hydroformylating an organic compound having an unsaturated bond according to any one of claims 1 to 5, which is performed at MPa.
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| JP3343585B2 true JP3343585B2 (en) | 2002-11-11 |
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Cited By (1)
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|---|---|---|---|---|
| WO2011027618A1 (en) | 2009-09-03 | 2011-03-10 | 日立化成工業株式会社 | Tricyclodecane monomethanol monocarboxylic acid and derivatives thereof |
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|---|---|---|---|---|
| EP2837617B1 (en) | 2003-08-27 | 2015-12-23 | Mitsubishi Gas Chemical Company Inc. | Process for producing alicyclic aldehydes |
| WO2007111091A1 (en) | 2006-03-28 | 2007-10-04 | Hitachi Chemical Company, Ltd. | Method for producing alcohol by using carbon dioxide as raw material |
| KR101583846B1 (en) * | 2007-09-25 | 2016-01-08 | 히타치가세이가부시끼가이샤 | Method for producing alcohol using carbon dioxide as raw material |
| JP5586030B2 (en) * | 2009-10-22 | 2014-09-10 | 日立化成株式会社 | Method for producing tricyclodecane monomethanol monocarboxylic acid derivative |
| DE102010030209A1 (en) * | 2010-06-17 | 2011-12-22 | Evonik Oxeno Gmbh | Energy-efficient synthesis of aliphatic adhehydrates from alkanes and carbon dioxide |
| JP7291387B2 (en) * | 2019-07-05 | 2023-06-15 | 国立研究開発法人産業技術総合研究所 | Catalyst for hydroformylation reaction using carbon dioxide as raw material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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