JPH0714892B2 - Method for producing aromatic aldehydes - Google Patents
Method for producing aromatic aldehydesInfo
- Publication number
- JPH0714892B2 JPH0714892B2 JP2064813A JP6481390A JPH0714892B2 JP H0714892 B2 JPH0714892 B2 JP H0714892B2 JP 2064813 A JP2064813 A JP 2064813A JP 6481390 A JP6481390 A JP 6481390A JP H0714892 B2 JPH0714892 B2 JP H0714892B2
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- present
- metal complex
- reaction
- group
- 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 - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は芳香族アルデヒド類の製造方法に関するもので
ある。TECHNICAL FIELD The present invention relates to a method for producing aromatic aldehydes.
芳香族アルデヒドは医薬、農薬、香料あるいは染料の合
成中間体として重要な物質である。Aromatic aldehydes are important substances as synthetic intermediates for medicines, agricultural chemicals, fragrances and dyes.
［従来の技術］ 従来より、芳香族アルデヒド類を製造する方法は種々知
られている。例えば塩化ベンザールを加水分解する方
法、塩化ベンゾイルを還元する方法、安息香酸を還元す
る方法、錯体触媒存在下、芳香族ハロゲン化物と水性ガ
スを反応させる方法あるいは芳香族炭化水素とオキシ塩
化リンおよびジメチルホルムアミドを反応させる方法
（Vilsmeyer反応）などがある。[Prior Art] Various methods for producing aromatic aldehydes have been conventionally known. For example, a method of hydrolyzing benzal chloride, a method of reducing benzoyl chloride, a method of reducing benzoic acid, a method of reacting an aromatic halide with water gas in the presence of a complex catalyst, or an aromatic hydrocarbon with phosphorus oxychloride and dimethyl. There is a method of reacting formamide (Vilsmeyer reaction).
しかしながら、これらの方法は、比較的高価で入手し難
い原料を使用せねばならない点などの問題点を有し、工
業的実施の観点からは満足できるものではない。そのた
め、より安価で入手安易である芳香族炭化水素類を原料
とし、直接芳香族アルデヒドを合成する方法が望まれ
る。本発明者等の一部は、錯体触媒と光照射との組合せ
により、芳香族炭化水素類を直接的にカルボニル化反応
処理して対応する芳香族アルデヒド等に変換する方法を
見い出した。（特開昭64−6222） ［発明が解決しようとする課題］ しかしながら、かかる方法では触媒活性が低いため十分
高い生産性が得られず、工業的製造法としては十分に満
足できるものではなかった。すなわち、本発明の目的は
芳香族炭化水素類を原料として用い、光照射下で直接的
にカルボニル化反応処理を行い芳香族アルデヒドを高い
生産性で製造する方法を提供することにある。However, these methods have problems such as the fact that relatively expensive and hard to obtain raw materials must be used, and they are not satisfactory from an industrial viewpoint. Therefore, there is a demand for a method of directly synthesizing an aromatic aldehyde from a cheaper and easily available aromatic hydrocarbon as a raw material. Some of the present inventors have found a method of converting an aromatic hydrocarbon to a corresponding aromatic aldehyde by directly subjecting an aromatic hydrocarbon to a carbonylation reaction by a combination of a complex catalyst and light irradiation. (Japanese Patent Application Laid-Open No. 64-6222) [Problems to be solved by the invention] However, since the catalyst activity is low in such a method, sufficiently high productivity cannot be obtained, and it is not sufficiently satisfactory as an industrial production method. . That is, an object of the present invention is to provide a method for producing an aromatic aldehyde with high productivity by using an aromatic hydrocarbon as a raw material and directly performing a carbonylation reaction treatment under light irradiation.
［課題を解決するための手段］ そこで、本発明者等はかかる問題点を解決するべく鋭意
検討を行った結果、錯体触媒における配位コイルとして
立体的かさ高さが小さく、かつ電子供与性の高い特定構
造のホスフィンを用いることにより、従来の問題点が解
消されることを見いだし本発明に到達した。すなわち、
本発明の課題は芳香族炭化水素類を遷移金属錯体の存在
下および光照射下において一酸化炭素と反応させる方法
において、遷移金属錯体の配位子のうち少なくとも１つ
が一般式 （式中、R1−R9は水素原子、アルキル基、アリール基、
アラルキル基またはシクロアルキル基を示し、それらは
互いに同じであっても異なっていても良い。）で表され
るホスホラン類を用いることにより容易に達成される。[Means for Solving the Problems] Therefore, the inventors of the present invention have conducted diligent studies to solve such problems, and as a result, have found that the coordination coil in the complex catalyst has a small steric bulk and an electron donating property. The present inventors have found that the conventional problems can be solved by using a phosphine having a high specific structure, and have reached the present invention. That is,
An object of the present invention is to provide a method of reacting aromatic hydrocarbons with carbon monoxide in the presence of a transition metal complex and under irradiation of light, wherein at least one of the ligands of the transition metal complex has the general formula (In the formula, R 1 to R 9 are a hydrogen atom, an alkyl group, an aryl group,
It represents an aralkyl group or a cycloalkyl group, which may be the same or different from each other. ) Is easily achieved by using the phosphoranes represented by
以下に本発明をさらに詳細に説明する。The present invention will be described in more detail below.
本発明の製造方法に供しうる芳香族炭化水素類は、その
芳香環に少なくとも１つの水素原子が結合しているもの
であれば如何なるものでも用いることができる。これら
を具体的に例示すれば、ベンゼン、トルエン、イソプロ
ピルベンゼン、ｔ−ブチルベンゼン、イソブチルベンゼ
ン、キシレン、ナフタレン、メチルナフタレン、クロル
ベンゼン、アニソール、ジフェニルエーテル、安息香酸
メチル等が挙げられる。As the aromatic hydrocarbons that can be used in the production method of the present invention, any aromatic hydrocarbons can be used as long as at least one hydrogen atom is bonded to the aromatic ring. Specific examples thereof include benzene, toluene, isopropylbenzene, t-butylbenzene, isobutylbenzene, xylene, naphthalene, methylnaphthalene, chlorobenzene, anisole, diphenyl ether, and methyl benzoate.
本発明で用いる遷移金属錯体触媒において、その遷移金
属成分としては、特に第８族遷移金属を用いるのが好ま
しい。具体的には、特にロジウムの使用が好適である。
その他、イリジウム、鉄、コバルト、ルテニウム、白金
等の遷移金属の使用も可能である。In the transition metal complex catalyst used in the present invention, it is particularly preferable to use a Group 8 transition metal as the transition metal component. Specifically, the use of rhodium is particularly preferable.
In addition, transition metals such as iridium, iron, cobalt, ruthenium and platinum can also be used.
本発明で用いる好ましい遷移金属錯体を例示すると、一
般式RhXL3（Ｘはハロゲン原子、Ｌは配位子を示す。以
下同様の意味を表わす。）、RhX(CO)L2、HRh(CO)L3、HR
h(CO)2L2、IrXL3、IrX(CO)L2、IrH5L2、IrH3(CO)L2、C
p′RhH2L（Cp′：ペンタメチルシクロペンタジエニルを
示す。以下同様である。）、Cp′IrH2L、Co2(CO)6L2、C
pCoX2L（Cp:シクロペンタジエニルを示す。以下同様で
ある。）、CoX2L2、CoXL3、CoH3L3、CpCoL2、Ru(CO)3L2
などが挙げられるが、これらに制限されるものではな
い。Examples of the preferred transition metal complex used in the present invention include the general formula RhXL 3 (X represents a halogen atom, L represents a ligand, and the same meanings below), RhX (CO) L 2 and HRh (CO). L 3 , HR
h (CO) 2 L 2 , IrXL 3 , IrX (CO) L 2 , IrH 5 L 2 , IrH 3 (CO) L 2 , C
p′RhH 2 L (Cp ′: pentamethylcyclopentadienyl, the same shall apply hereinafter), Cp′IrH 2 L, Co 2 (CO) 6 L 2 , C
pCoX 2 L (Cp: indicates cyclopentadienyl; the same applies hereinafter), CoX 2 L 2 , CoXL 3 , CoH 3 L 3 , CpCoL 2 , Ru (CO) 3 L 2
However, the present invention is not limited to these.
また、これらの遷移金属錯体を単独でなく２種以上を共
存させて実施させてもよい。Further, these transition metal complexes may be carried out not alone but in combination of two or more kinds.
遷移金属錯体触媒の配位子Ｌは、その少なくとも１つが
一般式 （式中、R1−R9は水素原子、アルキル基、アリール基、
アラルキル基またはシクロアルキル基を示し、それらは
互いに同じであっても異なっていても良い。）で表され
るホスホラン類である。なお、前記一般式で示される配
位子に於て、アルキル基、アラルキル基、シクロアルキ
ル基の炭素数は特に制約されないが、通常その炭素数は
20以下である。また、該遷移金属錯体は前記ホスホラン
類以外の他の配位子を含んでいてもよく、これらの他の
配位子としてはトリメチルホスフィン、トリエチルホス
フィン、トリブチルホスフィン、トリオクチルホスフィ
ン、トリシクロヘキシルホスフィン、トリフェニルホス
フィン、トリベンジルホスフィン等が挙げられる。これ
らの配位子を前記ホスホラン類を含む遷移金属錯体に添
加して反応させることもでき、また、これらの配位子を
含む遷移金属錯体に前記ホスホラン類を添加して反応さ
せることも出来る。At least one of the ligands L of the transition metal complex catalyst has the general formula (In the formula, R 1 to R 9 are a hydrogen atom, an alkyl group, an aryl group,
It represents an aralkyl group or a cycloalkyl group, which may be the same or different from each other. ) Is a phosphorane represented by. In the ligand represented by the general formula, the number of carbon atoms of the alkyl group, aralkyl group, and cycloalkyl group is not particularly limited, but the number of carbon atoms is usually
20 or less. Further, the transition metal complex may contain a ligand other than the phosphoranes, and as the other ligands, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, Examples thereof include triphenylphosphine and tribenzylphosphine. These ligands can be added to the transition metal complex containing the phosphoranes to react with each other, or the phosphoranes can be added to the transition metal complex containing the ligands to react with each other.
本発明の反応は光の照射下において初めて効率的に進行
するが、その波長領域はいわゆる紫外、可視領域であれ
ばよく、水銀灯やキセノンランプの使用または太陽光等
による光照射が好ましく用いられる。またフィルターや
モノクロメータ等を使用して波長領域を制限したり、単
色光を照射することも可能である。特に好ましくは、30
0nm以上の波長領域の光を照射するのがよい。The reaction of the present invention proceeds efficiently only when irradiated with light, but its wavelength range may be in the so-called ultraviolet or visible range, and the use of a mercury lamp or a xenon lamp, or light irradiation with sunlight or the like is preferably used. It is also possible to limit the wavelength region using a filter, a monochromator or the like, or to irradiate monochromatic light. Particularly preferably, 30
It is preferable to irradiate light in the wavelength region of 0 nm or more.
本発明のカルボニル化反応では、反応温度としては特に
限定されるものではなく、反応速度を向上させる点で約
250℃程度まで加熱して行ってもよいが、通常０−200℃
で行うのがよい。一酸化炭素としては必ずしも単一なも
のを用いる必要はなく、反応に影響を与えないような不
活性ガスと共に用いてもよい。その際、一酸化炭素の圧
力としては特に限定されるものではなく、通常0.1−300
気圧、好ましくは0.5−100気圧の範囲で行うのがよい。
これらの範囲を越えると反応速度の点で好ましくない。In the carbonylation reaction of the present invention, the reaction temperature is not particularly limited, and it is about from the viewpoint of improving the reaction rate.
It may be heated up to about 250 ℃, but it is usually 0-200 ℃
It is good to do it in. It is not always necessary to use a single carbon monoxide, and it may be used together with an inert gas that does not affect the reaction. At that time, the pressure of carbon monoxide is not particularly limited and is usually 0.1-300.
Atmospheric pressure, preferably in the range of 0.5-100 atm.
Exceeding these ranges is not preferable in terms of reaction rate.
なお、本発明の反応は一般的に無溶媒でも実施される
が、原料化合物に比べカルボニル化されがたい各種溶媒
類を用いることも、本発明の有利な態様に含まれる。Although the reaction of the present invention is generally carried out without solvent, the use of various solvents that are less likely to be carbonylated than the starting compound is also included in an advantageous aspect of the present invention.
反応後の生成物の分離は未反応原料等を蒸留等で分離
後、精留、再結晶、クロマトグラフィー等に付すこと
で、容易に実施される。Separation of the product after the reaction is easily carried out by separating unreacted raw materials and the like by distillation and then subjecting them to rectification, recrystallization, chromatography and the like.
［効果］ 本発明によれば、安価かつ入手容易な芳香族炭化水素類
と一酸化炭素とから効率よく芳香族アルデヒド類が得ら
れ、その産業的意義は多大である。[Effects] According to the present invention, aromatic aldehydes can be efficiently obtained from inexpensive and easily available aromatic hydrocarbons and carbon monoxide, and their industrial significance is great.
［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が、本
発明はその要旨を越えない限り以下の実施例によって限
定されるものではない。[Examples] Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples without departing from the gist thereof.
実施例１ を0.7mM濃度で含むベンゼン30mlを、１気圧の一酸化炭
素雰囲気下、100Wの内部照射型高圧水銀灯を用いて光照
射し、室温で１時間反応させた。ガスクロマトグラフィ
ーにより分析した結果、ベンズアルデヒドがロジウム錯
体基準で541％の収率で生成していることが確認され
た。（Meはメチル基を表わし、以下同様の意味を有す
る）。Example 1 Was irradiated with 30 ml of benzene containing 0.7 mM of H2O at a concentration of 1 atm using a 100 W internal irradiation type high pressure mercury lamp and reacted at room temperature for 1 hour. As a result of analysis by gas chromatography, it was confirmed that benzaldehyde was produced in a yield of 541% based on the rhodium complex. (Me represents a methyl group and has the same meaning below).
実施例２ を用いて実施例１と同様の反応を行った結果、ベンズア
ルデヒドが391％/Rhの収率で生成した。Example 2 As a result of performing the same reaction as in Example 1 using benzaldehyde, benzaldehyde was produced in a yield of 391% / Rh.
実施例３ 実施例１の反応を14時間行った結果、ベンズアルデヒド
が4709％/Rhの収率で生成した。他にベンジルアルコー
ルが767％/Rhの収率で生成した。Example 3 As a result of carrying out the reaction of Example 1 for 14 hours, benzaldehyde was produced in a yield of 4709% / Rh. Other benzyl alcohol was produced in a yield of 767% / Rh.
比較例 に代えて、RhCl(CO)(PMe3)2を用いて実施例１と同様の
反応を行った結果、ベンズアルデヒドが385％/Rhの収率
で生成した。Comparative example Instead of RhCl (CO) (PMe 3 ) 2 , the same reaction as in Example 1 was carried out, and as a result, benzaldehyde was produced in a yield of 385% / Rh.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐々木 康之 神奈川県横浜市緑区鴨志田町1000番地 三 菱化成株式会社総合研究所内 審査官 本堂 裕司 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuyuki Sasaki 1000, Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd.
Claims (1)
および光照射下において一酸化炭素と反応させる方法に
おいて、遷移金属錯体の配位子のうち少なくとも１つが
一般式 （式中、R1−R9は水素原子、アルキル基、アリール基、
アラルキル基またはシクロアルキル基を示し、それらは
互いに同じであっても異なっていても良い。）で表され
るホスホラン類であることを特徴とする芳香族アルデヒ
ド類の製造方法。1. A method of reacting aromatic hydrocarbons with carbon monoxide in the presence of a transition metal complex and under irradiation of light, wherein at least one of the ligands of the transition metal complex has the general formula: (In the formula, R 1 to R 9 are a hydrogen atom, an alkyl group, an aryl group,
It represents an aralkyl group or a cycloalkyl group, which may be the same or different from each other. ) The method for producing an aromatic aldehyde, which is a phosphorane represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2064813A JPH0714892B2 (en) | 1990-03-15 | 1990-03-15 | Method for producing aromatic aldehydes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2064813A JPH0714892B2 (en) | 1990-03-15 | 1990-03-15 | Method for producing aromatic aldehydes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03264546A JPH03264546A (en) | 1991-11-25 |
| JPH0714892B2 true JPH0714892B2 (en) | 1995-02-22 |
Family
ID=13269062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2064813A Expired - Fee Related JPH0714892B2 (en) | 1990-03-15 | 1990-03-15 | Method for producing aromatic aldehydes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0714892B2 (en) |
-
1990
- 1990-03-15 JP JP2064813A patent/JPH0714892B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03264546A (en) | 1991-11-25 |
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