JP2857628B2 - Method for producing high content of epi-isomer of methyl jasmonate - Google Patents
Method for producing high content of epi-isomer of methyl jasmonateInfo
- Publication number
- JP2857628B2 JP2857628B2 JP25670089A JP25670089A JP2857628B2 JP 2857628 B2 JP2857628 B2 JP 2857628B2 JP 25670089 A JP25670089 A JP 25670089A JP 25670089 A JP25670089 A JP 25670089A JP 2857628 B2 JP2857628 B2 JP 2857628B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl jasmonate
- epi
- isomer
- jasmonate
- high content
- 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
Landscapes
- Fats And Perfumes (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、香料として有用なジャスモン酸メチルのエ
ピ体の高含有率物の製造方法に関し、更に詳しくは、本
発明はジャスモン酸メチルまたは、ジャスモン酸メチル
のエピ体を少量含むジャスモン酸メチルを加熱反応する
ことにより、容易にジャスモン酸メチルのエピ体の濃度
を高めることができるものである。The present invention relates to a method for producing a high content of an epi-form of methyl jasmonate useful as a fragrance, and more specifically, the present invention relates to a method for producing methyl jasmonate or By heating and reacting methyl jasmonate containing a small amount of methyl jasmonate epi-form, the concentration of methyl jasmonate epi-form can be easily increased.
［従来の技術］ ジャスモン酸メチルは、他の香料と広く調和するもの
であって、多くの花香調のベース香料に添加されてい
る。そして、その製造方法については多くの報告があ
る。しかし、近年ジャスモン酸メチルの香気についての
研究で、ジャスモン酸メチルと、ジャスモン酸メチルの
エピ体との間で平衡があり、不安定型のジャスモン酸メ
チルのエピ体が、安定型のジャスモン酸メチルよりも40
0倍も香気が強いことがわかり（T.E.Acree et.al.,J.Ag
ric.Food Chem.,33,425〜427,1985）、ジャスモン酸メ
チルのエピ体の合成に関しての研究が盛んに行われてい
る。[Related Art] Methyl jasmonate is widely harmonized with other fragrances, and is added to many flowery base fragrances. And there are many reports about the manufacturing method. However, in recent studies on the aroma of methyl jasmonate, there is an equilibrium between methyl jasmonate and the epi-form of methyl jasmonate, and the unstable epi-form of methyl jasmonate is more stable than the stable form of methyl jasmonate. Also 40
It turns out that the aroma is 0 times stronger (TEAcree et.al., J. Ag
ric. Food Chem., 33, 425-427, 1985), and studies on the synthesis of epi-forms of methyl jasmonate have been actively conducted.
ジャスモン酸メチル及びジャスモン酸メチルのエピ体
は、天然抽出物中に含まれてはいるものの含有率が低
く、単離するには分離精製に多くの工程が必要となり、
大量にジャスモン酸メチル及びジャスモン酸メチルのエ
ピ体を得ることは不可能である。Methyl jasmonate and the epi-isomer of methyl jasmonate, although contained in the natural extract, have a low content, and require many steps for separation and purification to isolate,
It is impossible to obtain methyl jasmonate and epi-forms of methyl jasmonate in large quantities.
一方、ジャスモン酸メチルの合成方法は古くから知ら
れており、最近ジャスモン酸メチルのエピ体の選択的合
成方法も検討されている（割田ら，第30回 香料・テル
ペンおよび精油化学に関する討論会,101,1986）。しか
し、これらの選択的合成方法は多工程にわたり、収率も
低いため、とても工業化できるものではなかった。さら
に、ジャスモン酸メチルとジャスモン酸メチルのエピ体
の混合物の蒸留分画でジャスモン酸メチルのエピ体を20
％含むものを得たり、アルカリや酸処理によりジャスモ
ン酸メチルのエピ体の含有率を８％程度に高めたものが
得られることが知られている。しかしながら、これらの
製造方法においても、蒸留等の工程をとらなければなら
ず非常に繁雑なものであった。On the other hand, a method for synthesizing methyl jasmonate has been known for a long time, and a method for selectively synthesizing epi-forms of methyl jasmonate has recently been studied (Cottada et al., The 30th Symposium on Flavors / Terpenes and Essential Oil Chemistry, 101,1986). However, these selective synthesis methods were not industrially applicable due to the multi-step and low yield. Further, the epi-form of methyl jasmonate was subjected to distillation fractionation of a mixture of methyl jasmonate and the epi-form of methyl jasmonate to obtain 20 epi-forms of methyl jasmonate.
It is known to obtain a compound containing methyl jasmonate with an epi-content of about 8% by alkali or acid treatment. However, even in these production methods, steps such as distillation have to be taken, which is very complicated.
［発明が解決しようとする課題］ 本発明者らは、このような事情に鑑み、鋭意研究を重
ねた結果、ジャスモン酸メチル単独または、ジャスモン
酸メチルのエピ体との混合物を加熱反応することにより
ジャスモン酸メチルのエピ体を容易そして安定に大量製
造できる方法を見出し、本発明を完成するに至った。[Problems to be Solved by the Invention] In view of such circumstances, the present inventors have conducted intensive studies and found that methyl jasmonate alone or a mixture thereof with an epi-form of methyl jasmonate was heated and reacted. The present inventors have found a method for easily and stably mass-producing an epi-isomer of methyl jasmonate, and have completed the present invention.
［課題を解決するための手段］ すなわち、本発明は、下記一般式（Ｉ）で示されるジ
ャスモン酸メチルまたは、該ジャスモン酸メチルと下記
一般式（II）で示されるジャスモン酸メチルのエピ体と
の混合物を30℃〜100℃で加熱反応させることにより得
られるジャスモン酸メチルのエピ体を６〜８％含む、ジ
ャスモン酸メチルとジャスモン酸メチルのエピ体との混
合物の製造方法である。[Means for Solving the Problems] That is, the present invention relates to methyl jasmonate represented by the following general formula (I) or an epi-form of methyl jasmonate and methyl jasmonate represented by the following general formula (II) Is a method for producing a mixture of methyl jasmonate and an epi-form of methyl jasmonate, which comprises 6 to 8% of an epi-form of methyl jasmonate obtained by heating and reacting the mixture at 30 ° C to 100 ° C.
本発明に用いられるジャスモン酸メチルは、上記一般
式（Ｉ）で表わされ、ジャスモン酸メチルのエピ体は、
上記一般式（II）で表わされる。本発明のこれらの化合
物は、天然物より抽出して得たものでも、合成して得た
ものでもかまわない。 The methyl jasmonate used in the present invention is represented by the above general formula (I).
It is represented by the above general formula (II). These compounds of the present invention may be those obtained by extraction from natural products or those obtained by synthesis.
本発明においては、ジャスモン酸メチルを単独で、ま
たはエピ体を少量、例えば１〜５％程度含むジャスモン
酸メチルを加熱反応させて、エピ体高含有率物を容易に
製造することができる 本発明においては、ジャスモン酸メチルまたは、ジャ
スモン酸メチルとジャスモン酸メチルのエピ体の混合物
を30℃〜100℃で熱反応させるものである。30℃より温
度が低いと反応時間が長くかかり、200℃より温度が高
いと分解や異臭が発生したり、逆にエピ体が減少したり
するので好ましくない。In the present invention, a high content of epi-form can be easily produced by heating and reacting methyl jasmonate alone or methyl jasmonate containing a small amount of epi-form, for example, about 1 to 5%. Is to thermally react methyl jasmonate or a mixture of methyl jasmonate and an epi-isomer of methyl jasmonate at 30 ° C. to 100 ° C. If the temperature is lower than 30 ° C., the reaction time becomes longer.
本発明の熱反応は、ジャスモン酸メチル単独または、
ジャスモン酸メチルとジャスモン酸メチルのエピ体との
混合物をそのまま行っても、メタノール、エタノール、
アセトンなどの溶媒に溶解した状態で行っても良い。The thermal reaction of the present invention is methyl jasmonate alone or
Even if the mixture of methyl jasmonate and the epi-form of methyl jasmonate is directly used, methanol, ethanol,
It may be performed in a state of being dissolved in a solvent such as acetone.
［実施例］ 次に、実施例を挙げて本発明を詳細に説明する。な
お、本発明はこれらに限定されるものではない。EXAMPLES Next, the present invention will be described in detail with reference to examples. Note that the present invention is not limited to these.
実施例１、２ ジャスモン酸メチルのエピ体を約１％含むジャスモン
酸メチルとジャスモン酸メチルのエピ体の混合物をメタ
ノール中２％溶液として50℃、100℃で熱反応させて、
ガスクロマトグラフィでその変化を測定したところ、表
１に示すように徐々にジャスモン酸メチルのエピ体の濃
度が上昇し、６〜８％に上った。Examples 1 and 2 A mixture of methyl jasmonate and methyl jasmonate epi-form containing about 1% of epi-form of methyl jasmonate was thermally reacted at 50 ° C. and 100 ° C. as a 2% solution in methanol,
When the change was measured by gas chromatography, as shown in Table 1, the concentration of the methyl jasmonate epi-form gradually increased to 6 to 8%.
以上のように製造したものは、異臭もなく市販品の５
から10倍も強い香気を有していた。 The product manufactured as described above has no off-flavor and is commercially available 5
Had a fragrance ten times stronger than that of
［発明の効果］ 本発明は、ジャスモン酸メチル単独または、ジャスモ
ン酸メチルとジャスモン酸メチルのエピ体の混合物を加
熱反応させることにより、香気を容易に強めることがで
き、また、従来品よりも熱安定性に富むものを提供する
ことができる。[Effects of the Invention] The present invention can easily enhance the aroma by heating and reacting methyl jasmonate alone or a mixture of methyl jasmonate and an epi-isomer of methyl jasmonate, and can further enhance the thermal aroma. A product having high stability can be provided.
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 69/738 A ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)Continuation of the front page (58) Field surveyed (Int. Cl. 6 , DB name) C07C 69/738 A CA (STN) REGISTRY (STN)
Claims (1)
メチルまたは、該ジャスモン酸メチルと下記一般式（I
I）で示されるジャスモン酸メチルのエピ体との混合物
を30℃〜100℃で加熱反応させることにより得られるジ
ャスモン酸メチルのエピ体を６〜８％含む、ジャスモン
酸メチルとジャスモン酸メチルのエピ体との混合物の製
造方法。(1) Methyl jasmonate represented by the following general formula (I) or said methyl jasmonate and the following general formula (I)
Methyl jasmonate and methyl jasmonate epi-forms containing 6 to 8% of methyl jasmonate epi-forms obtained by heating and reacting a mixture of methyl jasmonate epi-form shown in I) at 30 ° C. to 100 ° C. A method for producing a mixture with the body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25670089A JP2857628B2 (en) | 1989-09-29 | 1989-09-29 | Method for producing high content of epi-isomer of methyl jasmonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25670089A JP2857628B2 (en) | 1989-09-29 | 1989-09-29 | Method for producing high content of epi-isomer of methyl jasmonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03118348A JPH03118348A (en) | 1991-05-20 |
| JP2857628B2 true JP2857628B2 (en) | 1999-02-17 |
Family
ID=17296262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25670089A Expired - Lifetime JP2857628B2 (en) | 1989-09-29 | 1989-09-29 | Method for producing high content of epi-isomer of methyl jasmonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2857628B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010101099A1 (en) | 2009-03-06 | 2010-09-10 | 株式会社資生堂 | Fragrance compositions |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011132359A (en) * | 2009-12-24 | 2011-07-07 | Shiseido Co Ltd | Fragrance composition |
| JP5589809B2 (en) * | 2010-12-03 | 2014-09-17 | 日本ゼオン株式会社 | Method for producing high epimer alkyl jasmonates |
-
1989
- 1989-09-29 JP JP25670089A patent/JP2857628B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| Ａｇｒｉｃ．Ｂｉｏｌ．Ｃｈｅｍ．（１９８８），５２（９），Ｐ．２２９９−２３０３ |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010101099A1 (en) | 2009-03-06 | 2010-09-10 | 株式会社資生堂 | Fragrance compositions |
| EP2687587A1 (en) | 2009-03-06 | 2014-01-22 | Takasago International Corporation | Fragrance compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03118348A (en) | 1991-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1076602A (en) | Alpha, beta-dialkyl conjugated nitriles | |
| US3879466A (en) | Bicyclo-{8 2.2.2{9 octa-5,7-dien-2-ones and a process for their preparation | |
| US4380675A (en) | 2,4-Dialkyl-2,6-heptadienal derivatives, a process for their preparation, and fragrant and flavoring products made therewith | |
| US3953377A (en) | Ethyl-2-trans-4-cis undecadienoate, ethyl-2-trans-4-cis dodecadienoate and ethyl-2-decadienoate perfume compositions | |
| JP2857628B2 (en) | Method for producing high content of epi-isomer of methyl jasmonate | |
| JP2610309B2 (en) | New fragrance | |
| JP2653027B2 (en) | 3- (Hexenyloxy) -propane-nitrile, method for producing the same, fragrance or fragrance composition | |
| JPH0737405B2 (en) | Novel aliphatic aldehyde | |
| JP2837210B2 (en) | Method for imparting, promoting, improving or changing the aroma characteristics of a fragrance composition or perfume product, perfume composition, perfume product, alicyclic ester and method for producing the same | |
| JPH0840970A (en) | Production of gingerol and shogaol | |
| JP2711893B2 (en) | Ketones and alcohols | |
| KR20100024964A (en) | 6,8,10-undecatrien-3-ol or 6,8,10-undecatrien-4-ol, and perfume composition | |
| JP3415678B2 (en) | Cyclohexene derivative | |
| US4392993A (en) | Alicyclic unsaturated compounds, their preparation and use of same as perfume ingredients | |
| JP3386596B2 (en) | Method for producing 5 (E), 8 (Z), 11 (Z) -tetradecatrien-2-one | |
| JPS61178977A (en) | Pyran derivative, production thereof and perfume composition containing same | |
| US4124644A (en) | Process for preparing substituted oxyacetaldehydes and acetals thereof | |
| EP0015412A2 (en) | Unsaturated macrocyclic ketones; their preparation; preparation of saturated macrocyclic ketones; application in perfume and flavour compositions of some unsaturated macrocyclic ketones | |
| US4196303A (en) | d-Isomenthoxyacetic acid | |
| IE41920B1 (en) | Process for the preparation of octadienenitrile compound | |
| JPH09500400A (en) | Substituted pyrazine manufacturing method | |
| JP2741091B2 (en) | 8-Methyl-4 (Z) -nonene derivative | |
| JPS6128671B2 (en) | ||
| US3974201A (en) | Methyl-N-(2-methyl-pentylidene)-anthranilate for perfume and flavoring compositions | |
| JP2609145B2 (en) | Aliphatic ketones and aliphatic alcohols |