JPS5843374B2 - Fuhouwaaldehyde Kagobutsuno Seizouhou - Google Patents
Fuhouwaaldehyde Kagobutsuno SeizouhouInfo
- Publication number
- JPS5843374B2 JPS5843374B2 JP48101415A JP10141573A JPS5843374B2 JP S5843374 B2 JPS5843374 B2 JP S5843374B2 JP 48101415 A JP48101415 A JP 48101415A JP 10141573 A JP10141573 A JP 10141573A JP S5843374 B2 JPS5843374 B2 JP S5843374B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- reaction
- present
- seizouhou
- kagobutsuno
- 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
Links
Description
【発明の詳細な説明】 本発明は不飽和アルデヒド化合物の製造法に関する。[Detailed description of the invention] The present invention relates to a method for producing unsaturated aldehyde compounds.
さらは詳しく述べるならば、本発明は一般式
（式中、ｎは１〜２の整数である）
で示されるアルコールド一般式
（式中 Ｂ／は低級アルキル基を表わす）で示される化
合物とを触媒の存在下に８０℃以上で加熱反応させるこ
とにより一般式
（式中、ｎは上記の意味を有する）
で示される不飽和アルデヒドを製造する方法に関する。More specifically, the present invention relates to alcohol compounds represented by the general formula (wherein, n is an integer of 1 to 2) and a compound represented by the general formula (wherein B/ represents a lower alkyl group). The present invention relates to a method for producing an unsaturated aldehyde represented by the general formula (wherein n has the above-mentioned meaning) by carrying out a heating reaction at 80° C. or higher in the presence of a catalyst.
本発明方法を反応式で示すならば次のとおりである。The reaction formula of the method of the present invention is as follows.
本発明において一般式（Ｉ）で示されるアルコールと一
般式（ＩＩ）で示される１−アルコキシ−３−メチルー
１．３−ブタジェンとの反応は、触媒の存在下８０℃以
上に加熱することにより、好ましくは酢酸第二水銀およ
び酢酸ナトリウムの如き適当な触媒の存在下、反応温度
８０〜１２０℃で不活性ガス雰囲気下にかきまぜること
により行うことができ、容易に収率よく目的の一般式（
２）で示される不飽和アルデヒド化合物を製造すること
ができる。In the present invention, the reaction between the alcohol represented by the general formula (I) and the 1-alkoxy-3-methyl-1,3-butadiene represented by the general formula (II) is carried out by heating to 80°C or higher in the presence of a catalyst. , preferably in the presence of a suitable catalyst such as mercuric acetate and sodium acetate, by stirring under an inert gas atmosphere at a reaction temperature of 80 to 120°C, and the desired general formula (
The unsaturated aldehyde compound shown in 2) can be produced.
なお、本反応では前記反応式に示したとおりアルコール
（Ｒ’ＯＨ）が副生ずるので、これを常圧あるいは減圧
下に反応中に系外へ取り出すことが望ましい。In this reaction, alcohol (R'OH) is produced as a by-product as shown in the above reaction formula, so it is desirable to take this out of the system under normal pressure or reduced pressure during the reaction.
本発明において反応溶媒は本質的には不要であるがトル
エン、キシレン、ジ−ｎ−ブチルエーテル、ｎ−オクタ
ンなどを溶媒として使市することは何ら支障を来たすも
のでない。Although a reaction solvent is essentially unnecessary in the present invention, there is no problem in using toluene, xylene, di-n-butyl ether, n-octane, etc. as a solvent.
次に本発明の特徴をわかりやすく代表例を挙げて説明す
る。Next, the features of the present invention will be explained in an easy-to-understand manner by giving representative examples.
まず一般式（１）で示されるアルコールとしてはイソプ
レンから簡単に誘導できるプレノールを用い、一般式（
ＩＩ）で示される化合物としてはやはりイソプレンの誘
導体である１−エトキシ−３−メチル−１，３−ブタジ
ェンを用いた場合、この両者を酢酸第二水銀および酢酸
ナトリウムの存在下に９５℃で数時間かきまぜるだけで
収率よくシトラールを製造することができる。First, as the alcohol represented by the general formula (1), prenol, which can be easily derived from isoprene, is used, and the general formula (
When 1-ethoxy-3-methyl-1,3-butadiene, which is also a derivative of isoprene, is used as the compound represented by II), both are mixed at 95°C in the presence of mercuric acetate and sodium acetate. Citral can be produced in good yield just by stirring for a long time.
これは香料あるいは医薬品としてのヨノンあるいはビタ
ミンＡなどの重要な合成中間体である。It is an important synthetic intermediate for ionone and vitamin A, which are used as fragrances or medicines.
従来シトラールは工業的には次のように製造されている
。Conventionally, citral has been industrially produced as follows.
すなわち、ジメチルビニルカルビノールにジケテンを反
応させ、まずＣ３伸長を行なったメチルへブテノンを得
、さらにエチニル化反応によりＣ２伸長を行ないデヒド
ロリナロールとしたのち触媒の存在下に熱処理すること
により得られる。That is, it is obtained by reacting dimethyl vinyl carbinol with diketene to obtain methylhebutenone which has undergone C3 extension, and then C2 extension by ethynylation reaction to obtain dehydrolinalool, which is then heat-treated in the presence of a catalyst.
この方法にくらべ、本発明方法１こよれば一段でしかも
極めて容易に収率よくシトラールを合成することができ
る。Compared to this method, according to the method 1 of the present invention, citral can be synthesized in a single step and extremely easily with good yield.
またこのシトラールのアルデヒド基の選択的還元により
得られるゲラニオールおよびネロールの混合物に対し、
さらに１−エトキシ−３−メチル−１，３−ブタジェン
を反応させると、さらにＣ６伸長されたβ型のファルネ
サールを得ることができる。Moreover, for the mixture of geraniol and nerol obtained by selective reduction of the aldehyde group of this citral,
Further, by reacting with 1-ethoxy-3-methyl-1,3-butadiene, further C6-extended β-type farnesal can be obtained.
このように本発明をくり返し行なうならば容易にポリプ
レニルアルデヒドが得られ、さらには香料、医薬品の重
要な中間体であるポリプレニルアルコールあるいはポリ
プレニルカルボン酸に誘導できる。If the present invention is repeated in this way, polyprenyl aldehyde can be easily obtained, and further it can be derived into polyprenyl alcohol or polyprenyl carboxylic acid, which are important intermediates for perfumes and pharmaceuticals.
本発明に用いられる１−アルコキシ−３−アルキル−１
，３−ブタジェンの好ましい例は、１−メトキシ−３−
メチル−１，３−ブタジェン、１−エトキシ−３−メチ
ル−１，３−ブタジェンなどである。1-alkoxy-3-alkyl-1 used in the present invention
A preferred example of ,3-butadiene is 1-methoxy-3-
Examples include methyl-1,3-butadiene and 1-ethoxy-3-methyl-1,3-butadiene.
これらジエンエーテル化合物は一般ｔこ次に示されるア
セタール型の化合物の脱アルコールの方法により製造さ
れる。These diene ether compounds are generally produced by the following method of dealcoholization of acetal type compounds.
（ただし Ｂ ／ 、 Ｂ ／／およびＲ″′はそれぞ
れ独立にメチル、エチル、プロピル、ブチル基などの低
級アルキル基を意味する）。(However, B / , B // and R'' each independently mean a lower alkyl group such as methyl, ethyl, propyl, butyl group).
また一般式（１）で示されるアルコールとしては３−メ
チル−２−ブテン−１−オール（プレノール）および３
，７−シメチルー２，６−オクタゲニン−１−オール（
ゲラニオール、ネロール）がある。In addition, examples of the alcohol represented by the general formula (1) include 3-methyl-2-buten-1-ol (prenol) and 3-methyl-2-buten-1-ol (prenol).
,7-dimethyl-2,6-octagenin-1-ol (
geraniol, nerol).
次（こ実施例で本発明を具体的に説明する。The present invention will be specifically explained in the following example.
なお実施例中の部はすべて重要部を意味する。Note that all parts in the examples mean important parts.
実施例 Ｊ
プレノール０．８６部、１−エトキシ−３−メチル−１
，３−ブタジェン２．２４部、酢酸第二水銀０．２５部
および酢酸す） ＩＪウム０．１０部をアルゴンガス雰
囲気下に反応温度９５℃で８時間かきまぜた。Example J Prenol 0.86 parts, 1-ethoxy-3-methyl-1
, 2.24 parts of 3-butadiene, 0.25 parts of mercuric acetate, and 0.10 parts of IJ acetate were stirred at a reaction temperature of 95° C. for 8 hours under an argon gas atmosphere.
反応中に副生ずるエチルアルコールは常圧下に系外に留
去した。Ethyl alcohol produced as a by-product during the reaction was distilled out of the system under normal pressure.
得られた反応混合物のガスクロマトグラフィーによる分
析ではプレノールはほとんど完全に消費され、生成物の
ほとんどはシトラールであった。Analysis of the resulting reaction mixture by gas chromatography showed that prenol was almost completely consumed and most of the product was citral.
ガスクロマトグラフィーによる定量の結果、シトラール
の収率は仕込んだプレノールに対する理論収率に対して
７６％であった。As a result of quantitative determination by gas chromatography, the yield of citral was 76% of the theoretical yield based on the charged prenol.
実施例 ２
実施例１のプレノールの代りにゲラニオールを１．５４
部用いる以外は実施例１と同様に行ないβ型ファルネサ
ールを得た。Example 2 In place of prenol in Example 1, 1.54% of geraniol was used.
β-type farnesal was obtained in the same manner as in Example 1 except that
仕込んぞゲラニオールに対して６０％の収率であった。The yield was 60% based on the charged geraniol.
Claims (1)
合物とを触媒の存在下に８０℃以上で加熱反応させるこ
とにより一般式 （式中、ｎは上記の意味を有する） で示される化合物を得ることを特徴とする不飽和アルデ
ヒド化合物の製造法。[Claims] 1. An alcohol represented by the general formula (in the formula, %n is an integer of 1 to 2) and a compound represented by the general formula (in the formula, %R' represents a lower alkyl group) are catalyzed. 1. A method for producing an unsaturated aldehyde compound, which comprises obtaining a compound represented by the general formula (wherein n has the above meaning) by carrying out a heating reaction at 80° C. or higher in the presence of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP48101415A JPS5843374B2 (en) | 1973-09-07 | 1973-09-07 | Fuhouwaaldehyde Kagobutsuno Seizouhou |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP48101415A JPS5843374B2 (en) | 1973-09-07 | 1973-09-07 | Fuhouwaaldehyde Kagobutsuno Seizouhou |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5050301A JPS5050301A (en) | 1975-05-06 |
| JPS5843374B2 true JPS5843374B2 (en) | 1983-09-27 |
Family
ID=14300062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP48101415A Expired JPS5843374B2 (en) | 1973-09-07 | 1973-09-07 | Fuhouwaaldehyde Kagobutsuno Seizouhou |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5843374B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49125314A (en) * | 1973-03-12 | 1974-11-30 |
-
1973
- 1973-09-07 JP JP48101415A patent/JPS5843374B2/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49125314A (en) * | 1973-03-12 | 1974-11-30 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5050301A (en) | 1975-05-06 |
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