JPS604180B2 - Method for producing tetrahydro-4H-pyran-4-one - Google Patents
Method for producing tetrahydro-4H-pyran-4-oneInfo
- Publication number
- JPS604180B2 JPS604180B2 JP5809174A JP5809174A JPS604180B2 JP S604180 B2 JPS604180 B2 JP S604180B2 JP 5809174 A JP5809174 A JP 5809174A JP 5809174 A JP5809174 A JP 5809174A JP S604180 B2 JPS604180 B2 JP S604180B2
- Authority
- JP
- Japan
- Prior art keywords
- pyran
- tetrahydro
- methylene
- tetrahydropyran
- ozone
- 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
Landscapes
- Pyrane Compounds (AREA)
Description
【発明の詳細な説明】
本発明は４ーメチレンーテトラヒドロピランのオゾン酸
化・開裂反応によるテトラヒドロー』日−ピラン−４−
オンの製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides tetrahydro-pyran-4-
Regarding the manufacturing method of on.
テトラヒドロー』日一ピランー４ーオン
は食品香料であるマルトールの合成中間体として重要な
化合物であるが、これの製造法としては、従釆「 オー
ゥェェンら〔Ｇ．Ｒ．０冊ｎａｎｄＣ．ＢＲｅｅｓｅ、
Ｊ．Ｃｈｅｍ．Ｓｏｃへ（Ｃ）１９７０、２４０１〕の
方法が知られているにすぎない。Pyran-4-one is an important compound as an intermediate for the synthesis of maltol, a food flavoring agent.
J. Chem. Soc (C) 1970, 2401] is the only known method.
本発明者らはテトラヒドロー４Ｈ−ピラン−４−オンを
より安価に製造しうる方法を探究した結果、４ーメチレ
ンーテトラヒドロピランを出発原料とする方法に到達し
た。The present inventors searched for a method for producing tetrahydro-4H-pyran-4-one at a lower cost, and as a result, they arrived at a method using 4-methylene-tetrahydropyran as a starting material.
すなわち、本発明によれば、４−メチレンーテトラヒド
ロピランをオゾン酸化し、酸化生成物を還元分解するこ
とにより、テトラヒドロ‐岬‐ピランー４ーオンを高収
率で得ることができる。That is, according to the present invention, tetrahydro-misaki-pyran-4-one can be obtained in high yield by ozone-oxidizing 4-methylene-tetrahydropyran and reductively decomposing the oxidized product.
４−メチレンーテトラヒドロピランはイソブテンとホル
ムアルデヒドから４・４ージメチルーメタジオキサンを
経てィソプレンを合成する方法（この方法は現に工業的
規模で操業されている）において副産物として安価にし
かも容易に入手できる物質であり、したがってこれを高
収率でテトラヒドロ−』Ｈ‐ピラン−４−オンに変換す
ることができる本発明方法は前述の既知方法に比較して
工業的にはるかに有利な方法である。4-Methylene-tetrahydropyran can be obtained cheaply and easily as a by-product in the process of synthesizing isoprene from isobutene and formaldehyde via 4,4-dimethyl-metadioxane (this process is currently operated on an industrial scale). The process according to the invention, which can be converted into tetrahydro'H-pyran-4-one in high yields, is industrially much more advantageous compared to the previously mentioned known processes.
本発明に従って４ーメチレンーテトラヒドロピランをオ
ゾン酸化することはテトラヒドロ−凪ーピランー４ーオ
ンの高収率を達成するために極めて重要であり、オゾン
酸化にかえて−般の酸化方法を用いた場合には、４ーメ
チレンーテトラヒドロピランの特異な構造が原因して、
後述の参考例に示すようにテトラヒドロー』Ｈ−ピラン
ー４ーオンの収率は著しく低くなる。Ozone oxidation of 4-methylene-tetrahydropyran according to the present invention is extremely important for achieving high yields of tetrahydro-nagi-pyran-4-one, and when conventional oxidation methods are used instead of ozone oxidation, is caused by the unique structure of 4-methylene-tetrahydropyran.
As shown in the Reference Examples below, the yield of tetrahydro'H-pyran-4-one becomes extremely low.
本発明に従う４ーメチレンーテトラヒドロピランのオゾ
ン酸化は、４−メチレンーテトラヒドロピランまたはこ
れを溶剤で希釈した溶液中へオゾンを含有する空気また
は酸素を通じることによって行うことができる。Ozone oxidation of 4-methylene-tetrahydropyran according to the present invention can be carried out by passing ozone-containing air or oxygen through 4-methylene-tetrahydropyran or a solution thereof diluted with a solvent.
溶剤としては炭化水素、ハロゲン化炭化水素、脂肪酸、
脂肪酸ェステル、脂肪族ケトン類などが使用できる。オ
ゾン酸化時の反応温度は一７８℃〜十２０℃、好ますく
は一６び０〜−２０ｑｏである。この反応は著しい発熱
を伴うので、冷却に注意し、なるべく温度を一定に保つ
ことが望ましい。オゾン酸化生成物（オゾニド）は不安
定であって長時間経過すると異常分解を起すこともある
ので、可能な限り速やかに還元分解することが好ましい
。生成オゾニドの還元分解は二酸化硫黄、亜硫酸塩、フ
ェロシアン化カリウム、水素化アルミニウムリチウムな
どの還元剤、または有機酸と亜鉛末の組合せなどを用い
て無触媒下に行うことができるほかに、白金、パラジウ
ムなどの水素添加触媒の存在下に水素と反応させる接触
還元分解法によって行うこともでき、いずれの場合も良
好な結果を与える。Solvents include hydrocarbons, halogenated hydrocarbons, fatty acids,
Fatty acid esters, aliphatic ketones, etc. can be used. The reaction temperature during ozone oxidation is -78°C to 120°C, preferably 160 to -20 qo. Since this reaction is accompanied by significant heat generation, it is desirable to pay attention to cooling and keep the temperature as constant as possible. Since ozone oxidation products (ozonides) are unstable and may undergo abnormal decomposition over a long period of time, it is preferable to reductively decompose them as quickly as possible. Reductive decomposition of the generated ozonide can be carried out without a catalyst using a reducing agent such as sulfur dioxide, sulfite, potassium ferrocyanide, lithium aluminum hydride, or a combination of an organic acid and zinc dust. It can also be carried out by a catalytic reductive cracking method in which it is reacted with hydrogen in the presence of a hydrogenation catalyst such as, and good results are given in either case.
この還元分解を行う温度は、用いられる還元分解の方法
および還元剤または触媒によって好適な範囲を異にする
ことはあるが、一般に０℃〜１００ｏｏの範囲内である
。生成したテトラヒドｏ−凪‐ピラン‐４−オンはたと
えば蒸留のような通常一般の分離手段によって反応混合
物から分離収得することができる。以下、本発明を実施
例によって説明する。The temperature at which this reductive decomposition is performed is generally within the range of 0° C. to 100° C., although the preferable range may vary depending on the reductive decomposition method and reducing agent or catalyst used. The produced tetrahydro-o-nagi-pyran-4-one can be separated and obtained from the reaction mixture by conventional separation means such as distillation. Hereinafter, the present invention will be explained by examples.
実施例 １
２００偽客の四つロフラスコに１０．７夕の４−メチレ
ン−テトラヒドロピランを塩化メチレン１５０ｃｃに溶
かして入れ、これにオゾンを−５０００で吹き込んだ。Example 1 4-methylene-tetrahydropyran of 10.7 days was dissolved in 150 cc of methylene chloride and placed in a four-bottle flask made of 200 fake customers, and ozone was blown into the flask at -5000.
反応液が青色に着色してからなおも２０分間オゾンを送
入し、その後、余分のオゾンを追い出すために反応液の
青色が消えるまで酸素を送入した。次に、反応液を５０
０の（客の四つ口フラスコに移し、氷酢酸６０ｃｃ、蒸
留水２．１夕およびエチルエーテル６０ｃｃを加え、冷
却燈拝しつつ亜鉛末２０夕を加え、そのあと徐々に加熱
し４６ｑ０で１時間還流させた。After the reaction solution was colored blue, ozone was continued for 20 minutes, and then, in order to drive out excess ozone, oxygen was introduced until the blue color of the reaction solution disappeared. Next, add 50% of the reaction solution
0 (transfer to a customer's four-necked flask, add 60 cc of glacial acetic acid, 2.1 cc of distilled water and 60 cc of ethyl ether, add 20 cc of zinc powder while cooling, then gradually heat to 46 cc to 1 ml). Refluxed for an hour.
ヨード‐でんぷん紙で呈色しなかったので反応液を炉遇
し、雑澄はさらにエチルエーテルで還流させて洗浄した
。炉液と洗浄液の両者を一緒にして追い出し蒸留し、再
蒸留することにより、８６．１〜８７．５ｑｏ／６２〜
６１柳Ｈｇでテトラヒドロー４日ーピラン−４ーオン８
．８夕を得た（収率８１％）。実施例 ２
２００の｛の四つロフラスコに５，４夕の４ーメチレン
ーテトラヒドロピランを精製へキサン１００の‘に溶し
て入れ、一５００Ｃでオゾンを吹き込んだ。Since no color developed on iodine-starch paper, the reaction solution was heated in an oven, and the miscellaneous solution was further washed by refluxing with ethyl ether. 86.1~87.5qo/62~ by distilling both the furnace liquid and cleaning liquid together and redistilling.
Tetrahydro 4 days with 61 Yanagi Hg - Piran-4-one 8
．． 8 samples were obtained (yield 81%). Example 2 4-methylene-tetrahydropyran, dissolved in 100 g of purified hexane, was placed in a 200 g.
必要量のオゾンを吹き込んだ後、反応液を５００地の加
圧オートクレープに移し、エタノール１００の‘とパラ
ジウム炭素触媒（炭素に５％のパラジウムを裾持させた
触媒）５夕を加え、水素圧１３０〜１０ぴ気圧で水素の
吸収が止まるまで燈梓、反応させた。反応液から触媒を
吸引口別し、分離してテトラヒドロー４Ｈ−ピランー４
ーオン４．０夕を得た（収率７３％）。参考例
○｝ 硝酸酸化
４ーメチレンーテトラヒドロピラン１０．９夕を氷冷、
燈拝しながら、これに発煙硝酸（ｄ＝１．５２）１２．
９夕を２５〜２６こ○で４５分間かけて滴下した。After blowing in the required amount of ozone, the reaction solution was transferred to a pressurized autoclave made of 500 ml of ethanol, and 100 ml of ethanol and a palladium-carbon catalyst (a catalyst containing 5% palladium on carbon) were added, and hydrogen was added. The reaction was continued at a pressure of 130 to 10 atm until hydrogen absorption stopped. The catalyst is suctioned from the reaction solution and separated to obtain tetrahydro-4H-pyran-4.
A yield of 4.0% was obtained (yield 73%). Reference example○} Nitric acid oxidation 4-methylene-tetrahydropyran 10.9 minutes was ice-cooled.
While worshiping the light, add fuming nitric acid (d=1.52)12.
The solution was added dropwise over 45 minutes at 25 to 26 times over 9 days.
その後１８分間反応を続け、合計１時間の反応ののちに
反応液を氷水に投入し、炭酸ナトリウムで中和し、油層
と水層を分離し、油層をエチルエーテルで希釈したのち
水洗し、乾燥した。水層はエチルエーテルで抽出後、水
洗し、乾燥した。両液をあわせて蒸留し、テトラヒドロ
一組‐ピラン‐４‐オンを０．５タ得た。原料回収１．
６夕を差し引いた収率は５．３％であった。（２ー 過
マンガン酸カリウムによる酸化硫酸マグネシウムの飽和
水溶液１００叫にリン酸二水素ナトリウム二水塩１５９
、アセトン（過マンガン酸カリウムで処理済）１５０の
‘、４ーメチレンーテトラヒドロピラン１０．１夕を加
え、氷冷、燈拝しつつ、過マンガン酸カリウム２８９を
１夕ずつ５時間で加えた。After that, the reaction continued for 18 minutes, and after a total of 1 hour of reaction, the reaction solution was poured into ice water, neutralized with sodium carbonate, separated into an oil layer and an aqueous layer, and the oil layer was diluted with ethyl ether, washed with water, and dried. did. The aqueous layer was extracted with ethyl ether, washed with water, and dried. Both solutions were combined and distilled to obtain 0.5 ta of tetrahydro-pyran-4-one. Raw material recovery 1.
The yield after subtracting 6 days was 5.3%. (2 - 100 g of a saturated aqueous solution of magnesium sulfate oxide with potassium permanganate to 159 g of sodium dihydrogen phosphate dihydrate)
, 150 g of acetone (treated with potassium permanganate) and 10.1 g of 4-methylene-tetrahydropyran were added, and while cooling on ice and keeping the lights on, 289 g of potassium permanganate was added for 1 g each in 5 hours. .
この間２〜５℃に保った。このあとさらに０℃で１時間
鷹拝を続けたのち、炉過した。炉液および残笹をそれぞ
れエチルエーテルで抽出し、両抽出液をあわせ、硫酸マ
グネシウムで乾燥した。ついで減圧蒸留によりテトラヒ
ドロ−４Ｈ−ピラン−４−オン１．２夕を得た（収率１
２％）。‘３｝ 過マンガン酸カリウム一過ヨウ素酸カ
リウムによる酸化蒸留水３２０ｃｃに過ヨウ素酸カリウ
ム２５夕、過マンガン酸カリウム０．９夕、炭酸カリウ
ム３５．７夕を溶かし、機拝しながら、これに４−メチ
レン−テトラヒドロピラン３．１夕、第三級ブタノール
２０ｃｃおよび蒸留水３０ｃｃからなる溶液を３２ｏｏ
で１扮ご間で滴下した。During this time, the temperature was maintained at 2 to 5°C. After this, the mixture was further heated at 0°C for 1 hour, and then filtered. The furnace liquor and the remaining bamboo were each extracted with ethyl ether, and both extracts were combined and dried over magnesium sulfate. Then, 1.2 hours of tetrahydro-4H-pyran-4-one was obtained by distillation under reduced pressure (yield: 1
2%). '3} Oxidation with potassium permanganate - Potassium periodate Dissolve 25 mL of potassium periodate, 0.9 mL of potassium permanganate, and 35.7 mL of potassium carbonate in 320 cc of distilled water, and add to this with care. A solution consisting of 4-methylene-tetrahydropyran, 20 cc of tertiary butanol, and 30 cc of distilled water was mixed with 32 ml of
I dripped it every time.
反応後、反応液をェチルェーテルで抽出し、抽出液を水
洗「乾燥し、減圧蒸留してテトラヒドロー』Ｈ−ピラン
−４一オン０．９夕を得たく収率２８％）。（４ー 重
クロム酸カリウムによる酸化
重クロム酸カリウム４０．４夕を蒸留水３１０ｃｃに溶
かし、これに４ーメチレンーテトラヒドロピラン１０．
１夕を加え、縄拝しながら、濃硫酸５３．６夕を蒸留水
１００ｃｃで希釈したものを３０ｑｏで１時間４び分か
けて滴下した。After the reaction, the reaction solution was extracted with ethyl ether, the extract was washed with water, dried, and distilled under reduced pressure to obtain 0.9% H-pyran-4-one (yield 28%). Oxidation of potassium dichromate by oxidation of potassium dichromate (40.4 cm) was dissolved in 310 cc of distilled water, and 4-methylene-tetrahydropyran (10.4 cm) was dissolved in 310 cc of distilled water.
1 hour was added, and while stirring, 53.6 hours of concentrated sulfuric acid diluted with 100 cc of distilled water was added dropwise at 30 qo over 1 hour and 4 minutes.
Claims (1)
、ついで生成物を還元分解することを特徴とする、テト
ラヒドロ−４Ｈ−ピラン−４−オンの製造法。1. A method for producing tetrahydro-4H-pyran-4-one, which comprises ozonizing 4-methylene-tetrahydropyran and then reductively decomposing the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5809174A JPS604180B2 (en) | 1974-05-23 | 1974-05-23 | Method for producing tetrahydro-4H-pyran-4-one |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5809174A JPS604180B2 (en) | 1974-05-23 | 1974-05-23 | Method for producing tetrahydro-4H-pyran-4-one |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS50154258A JPS50154258A (en) | 1975-12-12 |
| JPS604180B2 true JPS604180B2 (en) | 1985-02-01 |
Family
ID=13074261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5809174A Expired JPS604180B2 (en) | 1974-05-23 | 1974-05-23 | Method for producing tetrahydro-4H-pyran-4-one |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS604180B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190033949A (en) | 2017-09-22 | 2019-04-01 | 대동공업주식회사 | Control lever assembly of combine |
-
1974
- 1974-05-23 JP JP5809174A patent/JPS604180B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190033949A (en) | 2017-09-22 | 2019-04-01 | 대동공업주식회사 | Control lever assembly of combine |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS50154258A (en) | 1975-12-12 |
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