JP3565444B2 - Separation method of primary alcohol component in vetiver oil - Google Patents
Separation method of primary alcohol component in vetiver oil Download PDFInfo
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- JP3565444B2 JP3565444B2 JP24785794A JP24785794A JP3565444B2 JP 3565444 B2 JP3565444 B2 JP 3565444B2 JP 24785794 A JP24785794 A JP 24785794A JP 24785794 A JP24785794 A JP 24785794A JP 3565444 B2 JP3565444 B2 JP 3565444B2
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- Prior art keywords
- primary alcohol
- vetiver oil
- alcohol component
- half ester
- oil
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Description
【０００１】
【産業上の利用分野】
本発明は、天然香料として有用なベチバー油中に存在するキー物質である一級アルコール成分を、熱履歴のかからない方法による効率的な分離方法に関する。
【０００２】
【従来の技術】
ベチバー（Ｖｅｔｉｖｅｒａ ｚｉｚａｎｉｏｉｄｅｓ Ｓｔａｐｆ）は、熱帯、亜熱帯各地に自生し、インド、ジャバ、セイロン、レユニオン島などで栽培され、この根の部分は特有の芳香を有している。ベチバー油は、この根の部分を水蒸気蒸留して得られる精油であり、高級調合香料やせっけん香料として広く使用されている。ベチバー油の品質は、その油中の成分であるベチベロールの含量が高いこと、土くさくない匂いのものが、高級とされている。しかしながら、ベチバー油そのままでは土くさく、また青くささもあるため、この匂いを除去したり、あるいはベチベロールの含量を高めたベチバー精製油が使用されている。
【０００３】
かかるベチバー精製油を得る方法としては、ベチバー油を減圧下に蒸留して得る方法、ベチバー油をケン化し、減圧下に蒸留して得る方法、あるいはベチバー油を無水酢酸と反応させて、一級アルコールを酢酸エステルとなし、減圧下に蒸留して該酢酸エステルを採取し、次いで加水分解して一級アルコールを主成分として含有するアルコール成分を採取する、などの方法が行われている。このようにして得られたアルコール成分は、ベチベロールを主成分として含有し、ウッディ、バルサミックな香気と残香性を有し、高級な香料素材として有用である。しかしながら、これらの方法では、高含量のベチベロールが得られないとか、あるいは蒸留による熱履歴のため、一部が樹脂化したり、焦げ臭がついたりして必ずしも満足できるものではなかった。
【０００４】
そこで、これらの問題点を解決するため、ベチバー油に無水コハク酸を反応させ、ベチバー油中の一級アルコール成分を該酸のハーフエステルとなし、蒸留により、低沸点部分を留去して該ハーフエステルを分離し、該ハーフエステルを加水分解して、ベチバー油中の一級アルコール成分を分離する方法の改善提案がなされている（特公平６ー５７８３５号公報）。
【０００５】
【発明が解決しようとする課題】
しかしながら、この改善提案においても、ハーフエステル形成後、ハーフエステル以外の低沸点成分を蒸留により分離採取する手段が採用されているため、熱履歴を避けることができず、得られた一級アルコール成分の香気に加熱臭を伴い、必ずしも満足できるものではない。
【０００６】
【課題を解決するための手段】
本発明者らは、かかる問題点を解決すべく熱履歴のかからない方法について鋭意研究を行ってきた。その結果、該無水コハク酸のハーフエステルを塩基性イオン交換樹脂と処理することにより、熱履歴のかからない方法で効率よく一級アルコール成分を分離採取できることを見出し本発明を完成した。
【０００７】
すなわち本発明は、ベチバー油に無水コハク酸を反応させて得られる一級アルコールのコハク酸のハーフエステルを、イオン交換樹脂に吸着せしめ、次いで脱着して得られる該ハーフエステルを加水分解することを特徴とする、ベチバー油中の一級アルコール成分の分離採取方法を提供するものである。
【０００８】
本発明を実施するには、まずベチバー油を有機溶媒の存在下もしくは不存在下に、ベチバー油中の一級アルコールをコハク酸と反応させてハーフエステルを合成する。反応は有機溶媒の存在下に行うのが好ましく、有機溶媒としては、例えばトルエン、ベンゼン、キシレンなどを例示することができ、これら有機溶媒の使用量には格別の制限はないが、例えばベチバー油に対して、通常約１〜５重量倍程度の範囲で使用される。反応温度は、有機溶媒の種類あるいは無溶媒の場合により適宜に選択すればよいが、一般的には、例えば約８０〜１２０℃程度の範囲で行うことができる。反応時間も適宜に選択すればよく、例えば約３〜６時間程度の範囲で行われる。反応は、無触媒で進行するので触媒は特に必要としないが、使用する場合の触媒としては、通常ハーフエステルを合成するのに用いられるオルトリン酸、リン酸、Ｐートルエンスルホン酸などが使用される。反応終了後は水洗して過剰の無水コハク酸を除き、粗製の一級アルコールのハーフエステルを得ることができる。
【０００９】
次に、得られた粗製の一級アルコールのハーフエステルを塩基性イオン交換樹脂に吸着せしめ、次いで脱着することにより高純度の該ハーフエステルを容易に分離採取することができる。塩基性イオン交換樹脂の吸着、脱着処理は、バッチ方式あるいはカラム方式のいずれでもよいが、カラム方式で行うのがより好ましい。カラム方式における該ハーフエステルの吸着方法は通常の方法で行えばよく、また脱着方法は、まず例えばトルエン、ヘキサン、ベンゼンのごとき炭化水素系の有機溶媒で非吸着物質を除去し、次いでメタノール、エタノールのごとき水溶性有機溶媒で非吸着物質を完全に除去する。その後、アルカリ水溶液でイオン交換樹脂に吸着された該ハーフエステルを脱着せしめる。必要により、脱着後含水アルコールで洗浄してもよい。使用する塩基性イオン交換樹脂としては、例えば、強塩基性陰イオン交換樹脂Ｉ型、強塩基性陰イオン交換樹脂ＩＩ型、弱陰イオン交換樹脂などを挙げることができる。脱着に用いるアルカリとしては、水酸化ナトリウム、水酸化カリウムなどが挙げられる。これらアルカリの水溶液の濃度は、一般的には約５〜２０％程度の範囲が使用される。脱着液は、例えばトルエンのごとき有機溶媒で該ハーフエステルを抽出し、溶媒を留去して一級アルコールのコハク酸ハーフエステルを高純度で採取することができる。
【００１０】
かくして得られた該ハーフエステルにアルカリを加え、加水分解を行って目的とするベチバー油中の一級アルコール成分を高純度で得ることができる。使用するアルカリとしては、例えば水酸化ナトリウム、水酸化カリウムなどが挙げられ、これらは通常水溶液として加えられ、その濃度は適宜選択すればよいが、通常は約５〜１０％程度の濃度範囲で使用される。生成したベチバー油中の一級アルコール成分は減圧下に蒸留して実質的に不純物のないベチバー中の一級アルコールを分離採取することができる。
【００１１】
【実施例】
以下に実施例を挙げて本発明を更に詳細に説明する。
実施例１
ベチバー油（ジャワ産）１０００ｇに無水コハク酸２２７ｇ、トルエン１０００ｇを加え、撹拌しながら１１０〜１１５℃で５時間反応した。反応終了後、反応生成物を、前処理を行った強塩基性陰イオン交換樹脂；ＩＲー２６（アンバーライト製）を充填したカラムに流し、ベチバー油中の一級アルコールのハーフエステルを吸着させる。次にトルエン１０００ｍｌ、エタノール１ｍｌを順次流し、非吸着オイルを除去する。次に１０％苛性ソーダ３６００ｇ、水５００ｇ、エタノール２０００ｍｌを順次流して脱着を行った。この脱着液にトルエン１０００ｍｌを加えて目的物を抽出し、トルエンを留去して、粗製の一級アルコール成分を２１５ｇを得た。この一級アルコール成分を減圧下に蒸留を行い、１０１〜１１２℃／０．１ｍｍＨｇの一級アルコール留分１７０ｇを得た。
得られた一級アルコール成分の香気は、従来製法で製造されたものに比べ、加熱臭がなく、優れたウッディ、バルサミックな香気を有していた。
【００１２】
【発明の効果】
本発明により得られたベチバー油の一級アルコール成分は、青くささ、土くささがなく、加えて加熱臭がなく、ソフトで優れたウッディ、バルサミックな香気を有し、高級香料の素材として利用できる。[0001]
[Industrial applications]
The present invention relates to an efficient method for separating a primary alcohol component, which is a key substance present in vetiver oil useful as a natural flavor, by a method that does not require heat history.
[0002]
[Prior art]
Vetiver (Vetivera zizanioides Stampf) grows naturally in tropical and subtropical areas and is cultivated in India, Java, Ceylon, Reunion Island and the like, and the root portion has a unique aroma. Vetiver oil is an essential oil obtained by steam distillation of the root portion, and is widely used as a high-grade blended flavor or a soap flavor. The quality of vetiver oil is considered to be high if it has a high content of vetiverol, a component in the oil, and a smell that is not earthy. However, vetiver oil as it is can be gritty and bluish, so refined vetiver oil is used which removes this odor or has an increased vetiverol content.
[0003]
Examples of a method for obtaining such vetiver refined oil include a method of obtaining vetiver oil by distillation under reduced pressure, a method of obtaining vetiver oil by saponification and distillation under reduced pressure, or a method of reacting vetiver oil with acetic anhydride to form a primary alcohol. , Which is then distilled under reduced pressure to collect the acetic ester, and then hydrolyzed to collect an alcohol component containing a primary alcohol as a main component. The alcohol component thus obtained contains vetiverol as a main component, has a woody, balsamic aroma and a residual scent, and is useful as a high-grade fragrance material. However, these methods are not always satisfactory because a high content of vetiverol cannot be obtained, or a part thereof becomes resinous or burnt due to heat history due to distillation.
[0004]
Therefore, in order to solve these problems, succinic anhydride is reacted with vetiver oil, the primary alcohol component in vetiver oil is converted to a half ester of the acid, and a low boiling point portion is distilled off by distillation to remove the half alcohol. There has been proposed an improvement in a method of separating an ester, hydrolyzing the half ester, and separating a primary alcohol component in vetiver oil (JP-B-6-57835).
[0005]
[Problems to be solved by the invention]
However, even in this improvement proposal, after the formation of the half ester, a means for separating and collecting low boiling components other than the half ester by distillation is employed, so that the heat history cannot be avoided, and the obtained primary alcohol component is not removed. Aroma is accompanied by a heated odor, which is not always satisfactory.
[0006]
[Means for Solving the Problems]
The present inventors have intensively studied a method in which a heat history is not applied in order to solve such a problem. As a result, it has been found that by treating the half ester of succinic anhydride with a basic ion exchange resin, a primary alcohol component can be efficiently separated and collected by a method that does not require heat history, and the present invention has been completed.
[0007]
That is, the present invention is characterized in that a succinic acid half ester of a primary alcohol obtained by reacting succinic anhydride with vetiver oil is adsorbed on an ion exchange resin, and then the half ester obtained by desorption is hydrolyzed. The present invention provides a method for separating and collecting a primary alcohol component in vetiver oil.
[0008]
In practicing the present invention, first, a half ester is synthesized by reacting a primary alcohol in vetiver oil with succinic acid in the presence or absence of vetiver oil. The reaction is preferably performed in the presence of an organic solvent.Examples of the organic solvent include toluene, benzene, xylene, and the like.The amount of these organic solvents is not particularly limited, and is, for example, vetiver oil. Is usually used in a range of about 1 to 5 times by weight. The reaction temperature may be appropriately selected depending on the type of the organic solvent or the case where no solvent is used. In general, the reaction temperature can be, for example, in the range of about 80 to 120 ° C. The reaction time may be appropriately selected, for example, about 3 to 6 hours. Since the reaction proceeds in the absence of a catalyst, a catalyst is not particularly required.However, as a catalyst to be used, orthophosphoric acid, phosphoric acid, P-toluenesulfonic acid and the like which are usually used for synthesizing a half ester are used. You. After the completion of the reaction, excess succinic anhydride is removed by washing with water to obtain a crude primary alcohol half ester.
[0009]
Next, the obtained crude primary alcohol half ester is adsorbed on a basic ion exchange resin and then desorbed, whereby the high purity half ester can be easily separated and collected. The adsorption and desorption treatment of the basic ion exchange resin may be either a batch method or a column method, but is more preferably performed by a column method. The adsorption method of the half ester in the column method may be performed by a usual method, and the desorption method is to first remove non-adsorbed substances with a hydrocarbon-based organic solvent such as toluene, hexane, and benzene, and then remove methanol and ethanol. Non-adsorbed substances are completely removed with a water-soluble organic solvent such as Thereafter, the half ester adsorbed on the ion exchange resin is desorbed with an aqueous alkali solution. If necessary, it may be washed with aqueous alcohol after desorption. Examples of the basic ion exchange resin used include strong basic anion exchange resin type I, strong basic anion exchange resin type II, and weak anion exchange resin. Examples of the alkali used for desorption include sodium hydroxide and potassium hydroxide. The concentration of these alkali aqueous solutions is generally in the range of about 5 to 20%. For the desorption liquid, the half ester is extracted with an organic solvent such as toluene, and the solvent is distilled off to obtain a succinic acid half ester of a primary alcohol with high purity.
[0010]
An alkali is added to the half ester thus obtained and hydrolysis is carried out to obtain a desired primary alcohol component in vetiver oil with high purity. As the alkali to be used, for example, sodium hydroxide, potassium hydroxide and the like can be mentioned. These are usually added as an aqueous solution, and the concentration may be appropriately selected, but is usually used in a concentration range of about 5 to 10%. Is done. The primary alcohol component in the produced vetiver oil can be distilled under reduced pressure to separate and collect the primary alcohol in vetiver having substantially no impurities.
[0011]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples.
Example 1
227 g of succinic anhydride and 1000 g of toluene were added to 1000 g of vetiver oil (produced in Java) and reacted at 110 to 115 ° C. for 5 hours with stirring. After completion of the reaction, the reaction product is allowed to flow through a column filled with a pretreated strongly basic anion exchange resin; IR-26 (manufactured by Amberlite) to adsorb a half ester of a primary alcohol in vetiver oil. Next, 1000 ml of toluene and 1 ml of ethanol are sequentially flowed to remove non-adsorbed oil. Next, 3600 g of 10% caustic soda, 500 g of water and 2000 ml of ethanol were successively flowed to perform desorption. 1000 ml of toluene was added to the desorbed solution to extract the target product, and toluene was distilled off to obtain 215 g of a crude primary alcohol component. This primary alcohol component was distilled under reduced pressure to obtain 170 g of a primary alcohol fraction at 101 to 112 ° C / 0.1 mmHg.
The obtained fragrance of the primary alcohol component had no woody odor and had an excellent woody and balsamic fragrance as compared with those produced by the conventional production method.
[0012]
【The invention's effect】
The primary alcohol component of the vetiver oil obtained according to the present invention has no blueness, no earthiness, has no heating odor, has a soft and excellent woody, balsamic fragrance, and can be used as a material of high-grade fragrance. .
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24785794A JP3565444B2 (en) | 1994-10-13 | 1994-10-13 | Separation method of primary alcohol component in vetiver oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24785794A JP3565444B2 (en) | 1994-10-13 | 1994-10-13 | Separation method of primary alcohol component in vetiver oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08109391A JPH08109391A (en) | 1996-04-30 |
| JP3565444B2 true JP3565444B2 (en) | 2004-09-15 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24785794A Expired - Fee Related JP3565444B2 (en) | 1994-10-13 | 1994-10-13 | Separation method of primary alcohol component in vetiver oil |
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| Country | Link |
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| JP (1) | JP3565444B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5324370B2 (en) * | 2008-09-18 | 2013-10-23 | 株式会社アカル | Deodorant and method for producing deodorant |
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1994
- 1994-10-13 JP JP24785794A patent/JP3565444B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH08109391A (en) | 1996-04-30 |
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