JPS5848546B2 - Cis-trans isomerization method for unsaturated alcohols - Google Patents
Cis-trans isomerization method for unsaturated alcoholsInfo
- Publication number
- JPS5848546B2 JPS5848546B2 JP9715280A JP9715280A JPS5848546B2 JP S5848546 B2 JPS5848546 B2 JP S5848546B2 JP 9715280 A JP9715280 A JP 9715280A JP 9715280 A JP9715280 A JP 9715280A JP S5848546 B2 JPS5848546 B2 JP S5848546B2
- Authority
- JP
- Japan
- Prior art keywords
- cis
- trans isomerization
- unsaturated alcohols
- trans
- light
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は不飽和アルコールのシスートランス異性化に関
する。DETAILED DESCRIPTION OF THE INVENTION This invention relates to the cis-trans isomerization of unsaturated alcohols.
詳しく言えば、不飽和アルコールのシス型とトランス型
との間の異性化を行なうに当り、メルカブタン類と少量
のラジカル開始剤の存在下に光照射することを特徴とす
る不飽和アルコールリンストランス異性化方法である。Specifically, unsaturated alcohol rinse trans isomerization is performed by irradiating light in the presence of mercaptans and a small amount of radical initiator to perform isomerization between cis and trans forms of unsaturated alcohol. It is a method of conversion.
本発明人等は先に特願昭５４−７４９３７において不飽
和化合物をメルカブタン類の存在下に光照射することに
より選択的にシスートランス異性化反応が起ることを明
らかにした。The present inventors previously revealed in Japanese Patent Application No. 74937/1987 that a cis-trans isomerization reaction occurs selectively by irradiating an unsaturated compound with light in the presence of mercabutanes.
該発明法は少量の高沸物を生成する以外は二重結合の異
動やＯＨ基の転位等の副反応が全くない為、反応後の目
的化合物の分離精製が容易で、且つ反応液が殆んど光を
吸収しない為、必要な光エネルギーは極めて少なく、光
反応装置も単純で設計が容易な極めて優れた不飽和アル
コールのシスートランス異性化法である。The method of the invention does not involve any side reactions such as movement of double bonds or rearrangement of OH groups other than producing a small amount of high-boiling substances, so it is easy to separate and purify the target compound after the reaction, and the reaction liquid is hardly consumed. It is an excellent method for cis-trans isomerization of unsaturated alcohols because it does not absorb any light, so the required light energy is extremely small, and the photo reaction equipment is simple and easy to design.
本発明人等はメルカブタンの存在下の光照射による不飽
和アルコールのシスートランス異性化について詳細に研
究した結果、更にラジカル開始剤を少量添加して光照射
することにより、シスートランス異性化は極めて速く進
行することを発見し、本発明を完成した。As a result of detailed research on cis-trans isomerization of unsaturated alcohols by light irradiation in the presence of mercabutane, the present inventors found that by adding a small amount of a radical initiator and irradiating with light, cis-trans isomerization is extremely rapid. The present invention was completed based on the discovery that this process can proceed.
本発明の実施に供せられる不飽和アルコールとしては例
えば、次のような不飽和アルコールを挙げることができ
る。Examples of unsaturated alcohols that can be used in the practice of the present invention include the following unsaturated alcohols.
３・７−ジメチル−７−ヒドロキシー２−オクテン−１
−オール、３・７−ジメチル−２・６一オクタジエン−
１−オール、３・７・１１−トリメチル−２・６・１０
−ドデカトリエン−１−オール、３・７・１１−トリメ
チル−１・６・１０ドデカトリエン−３−オール、３・
７・１１１５−テトラメチル−３−へキサデカテトラエ
ン−１−オール等が例示できる。3,7-dimethyl-7-hydroxy-2-octene-1
-ol, 3,7-dimethyl-2,6-octadiene-
1-ol, 3,7,11-trimethyl-2,6,10
-dodecatrien-1-ol, 3.7.11-trimethyl-1.6.10 dodecatrien-3-ol, 3.
Examples include 7.1115-tetramethyl-3-hexadecatetraen-1-ol.
本発明に使用するメルカブタン類としてはＣ１〜Ｃ１８
のアルキルメルカブタン類及びシクロヘキサンチオール
、シクロペンタンチオール等が適当である。The mercabutanes used in the present invention include C1 to C18.
Alkylmercabutanes, cyclohexanethiol, cyclopentanethiol, etc. are suitable.
また芳香族チオール等も使用できる。Aromatic thiols and the like can also be used.
メルカプタン類の添加量は不飽和アルコール１モルに対
し０．１〜５モルが適当である。The appropriate amount of mercaptans to be added is 0.1 to 5 moles per mole of unsaturated alcohol.
一般に添加量の多い方が若干選択率が高い。Generally, the higher the amount added, the higher the selectivity.
本発明で使用するラジカル開始剤としては、アゾインブ
チロニトリル（ＡＩＢＮ）、ペンゾイルパーオキシド（
ＢＰＯ）が良く、添加量はメルカプタン類１モルに対し
、０．０１ないし０．２モルの範囲が適当である。The radical initiators used in the present invention include azoin butyronitrile (AIBN), penzoyl peroxide (
BPO) is good, and the amount added is suitably in the range of 0.01 to 0.2 mol per 1 mol of mercaptans.
ラジカル開始剤添加の効果は大きく、シスートランス異
性化は極めて速く進行し条件によってはメルカブタン単
独の場合に比べ異性化速度は数倍に達する。The effect of adding a radical initiator is large, and cis-trans isomerization proceeds extremely quickly, and depending on the conditions, the isomerization rate can reach several times that of mercabutane alone.
ラジカル開始剤の添加により若干選択率は低下するが、
二重結合の移動や官能基の転位等の副反応を生ずること
は全くない。Although the selectivity decreases slightly due to the addition of a radical initiator,
No side reactions such as movement of double bonds or rearrangement of functional groups occur.
本発明を実施するに際しＯ℃〜５０℃の温度範囲ではメ
ルカブタン類とラジカル開始剤の共存下でも光照射しな
げればシスートランス異性化は極めて遅い。When carrying out the present invention, cis-trans isomerization is extremely slow in the temperature range of 0° C. to 50° C. even in the coexistence of mercabutanes and a radical initiator without light irradiation.
然るに光照射下のラジカル開始剤の添加はその機構は不
明であるが極めて顕著な効果を有し反応は速やかに進行
する。However, the addition of a radical initiator under light irradiation has a very significant effect, and the reaction proceeds quickly, although the mechanism is unknown.
本発明は工業的に極めて有用である。The present invention is extremely useful industrially.
反応液が殆んど光を吸収しない為、必要な光エネルギー
は極めて少なく、且つ反応が著しく早い為、高価な光源
及び光反応装置は単純で小型でよい。Since the reaction solution absorbs almost no light, the required light energy is extremely small, and the reaction is extremely fast, so the expensive light source and photoreaction device can be simple and small.
以下実施例により本発明の内容を示す。The content of the present invention will be illustrated below with reference to Examples.
実施例 １
ネロール（シスー３・７−シメ−ｆ−ルー２・６オクタ
ジエン−１−オール）とｎ−デシルメルカブタンをそれ
ぞれ０．０５モル／ｌの濃度になるように、またＡＩＢ
Ｎを０．００２５モル／ｌの濃度になるようにベンゼン
に溶解し、この溶液をパイレツクス管中で窒素パブリン
グした後、封じ、常温のもとに高圧水銀灯で光照射した
。Example 1 Nerol (cis-3,7-cyme-f-2,6-octadien-1-ol) and n-decylmercabutane were each added to a concentration of 0.05 mol/l and AIB
N was dissolved in benzene to a concentration of 0.0025 mol/l, and this solution was bubbled with nitrogen in a Pyrex tube, sealed, and irradiated with light from a high-pressure mercury lamp at room temperature.
照射終了後、反応液中のネロール及びゲラニオール（ト
ランス−３・７−ジメチル−２・６−オクタジエン−１
−オール）をガスクロマトグラフで定量した。After the irradiation, nerol and geraniol (trans-3,7-dimethyl-2,6-octadiene-1) were removed from the reaction solution.
-ol) was determined by gas chromatography.
光照射時間１０分でネロールの転化率５０％、ゲラニオ
ールの選択率８５％であった。When the light irradiation time was 10 minutes, the conversion rate of nerol was 50% and the selectivity of geraniol was 85%.
実施例 ２
ラジカル開始剤としてＡＩＢＮに代えてＢＰＯを使用し
た以外は実施例１と同様にしてネロールの光異性化を行
なった。Example 2 Nerol was photoisomerized in the same manner as in Example 1 except that BPO was used instead of AIBN as a radical initiator.
光照射時間３分でネロールの転化率４８％、ゲラニオー
ルの選択率９２％であった。At a light irradiation time of 3 minutes, the conversion rate of nerol was 48% and the selectivity of geraniol was 92%.
光照射時間１０分でネロールの転化率６２％、ゲラニオ
ールの選択率８５％であった。When the light irradiation time was 10 minutes, the conversion rate of nerol was 62% and the selectivity of geraniol was 85%.
実施例 ３
原料不飽和アルコールをシスーネロリドール（シスー３
・７・１１−トリメチル−１・６・１０−ドデカトリエ
ン−３−オール）とした以外は実施例２と同様にして光
異性化を行なった。Example 3 The raw material unsaturated alcohol was converted into cissunerolidol (cissu 3
Photoisomerization was carried out in the same manner as in Example 2, except that 7,11-trimethyl-1,6,10-dodecatrien-3-ol) was used.
光照射時間１０分でシスーネロリドールの転化率５４％
、トランスーネロリドールの選択率は９１％であった。Conversion rate of cissunerolidol was 54% after 10 minutes of light irradiation.
, the selectivity for transnerolidol was 91%.
参考例
ＢＰＯ無添加とした以外は実施例３と同様にしてシスー
ネロリドールの光異性化を行なった。Reference Example Cisune lolidol was photoisomerized in the same manner as in Example 3, except that BPO was not added.
光照射時間２０分でシスーネロリドールの転化率４３％
、トランスーネロリドールの選択率は９８％であった。Conversion rate of cissunerolidol was 43% after 20 minutes of light irradiation.
, the selectivity of trans-nerolidol was 98%.
Claims (1)
ールのシス型とトランス型との間の異性化反応を行なう
に際し、メルカブタン類と少量のラジカル開始剤の存在
下に光照射することを特徴とする不飽和アルコールのシ
スートランス異性化方法。1. When carrying out the isomerization reaction between the cis and trans forms of an unsaturated alcohol in which both the cis and trans forms are present, light irradiation is carried out in the presence of mercaptans and a small amount of radical initiator. A method for cis-trans isomerization of unsaturated alcohols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9715280A JPS5848546B2 (en) | 1980-07-16 | 1980-07-16 | Cis-trans isomerization method for unsaturated alcohols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9715280A JPS5848546B2 (en) | 1980-07-16 | 1980-07-16 | Cis-trans isomerization method for unsaturated alcohols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5724313A JPS5724313A (en) | 1982-02-08 |
| JPS5848546B2 true JPS5848546B2 (en) | 1983-10-28 |
Family
ID=14184589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9715280A Expired JPS5848546B2 (en) | 1980-07-16 | 1980-07-16 | Cis-trans isomerization method for unsaturated alcohols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5848546B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI119769B (en) | 2003-11-17 | 2009-03-13 | Kone Corp | Procedure for mounting a lift and lift |
| JP5150233B2 (en) * | 2007-12-14 | 2013-02-20 | 信越化学工業株式会社 | Process for preparing olefin compound geometric isomer composition |
-
1980
- 1980-07-16 JP JP9715280A patent/JPS5848546B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5724313A (en) | 1982-02-08 |
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