JP3247258B2 - Production method of (-)-8α, 13-epoxy-14,15,16-trinorrabane - Google Patents
Production method of (-)-8α, 13-epoxy-14,15,16-trinorrabaneInfo
- Publication number
- JP3247258B2 JP3247258B2 JP25732094A JP25732094A JP3247258B2 JP 3247258 B2 JP3247258 B2 JP 3247258B2 JP 25732094 A JP25732094 A JP 25732094A JP 25732094 A JP25732094 A JP 25732094A JP 3247258 B2 JP3247258 B2 JP 3247258B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- reaction
- epoxy
- trinorrabane
- 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 - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Pyrane Compounds (AREA)
- Cosmetics (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Fats And Perfumes (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、木様、アンバー様など
の香気香味を有し、香粧品用あるいは食品用の調合香料
素材として従来から利用されてきた下記式（１）BACKGROUND OF THE INVENTION The present invention relates to the following formula (1) which has an aromatic flavor such as wood or amber, and has been conventionally used as a compounded fragrance material for cosmetics or foods.
【０００２】[0002]
【化３】 Embedded image
【０００３】で表される（−）−８α，１３−エポキシ
−１４，１５，１６−トリノルラブダンの製法に関す
る。更に詳しくは、本発明は後記式（２）で表される
（−）−８α，１３−ジヒドロキシ−１４，１５，１６
−トリノルラブダンを有機溶媒中、ハロゲン化亜鉛と接
触環化反応させて、高収率、高純度に前記式（１）の化
合物を得ることができる新規製法に関する。The present invention relates to a method for producing (-)-8α, 13-epoxy-14,15,16-trinorraband represented by the formula: More specifically, the present invention provides (-)-8α, 13-dihydroxy-14,15,16 represented by the following formula (2).
The present invention relates to a novel production method capable of obtaining a compound of the formula (1) in high yield and high purity by subjecting trinollabdane to a catalytic cyclization reaction with zinc halide in an organic solvent.
【０００４】[0004]
【従来の技術】従来、前記式（１）の化合物の製造法に
ついては、いくつかの報告がなされている。例えば、後
記式（２）の化合物をピリジン中、塩化ｐ−トルエンス
ルホニルを用いて前記式（１）の化合物を得る方法[Hel
v.Chim.Acta,63,1932(1980)]、また、後記式（２）の化
合物を脱水剤としてｐ−トルエンスルホン酸を用いて前
記式（１）の化合物を製造する方法[Helv.Chim.Acta,7
2,996(1989)]等が提案されている。2. Description of the Related Art Conventionally, a method for producing a compound of the above formula (1) has been proposed.
Some reports have been made. For example, after
The compound of the formula (2) is dissolved in pyridine in p-toluene chloride.
Method for obtaining the compound of the above formula (1) using rufonyl [Hel
v.Chim.Acta,63, 1932 (1980)] and the formula (2) below
Using p-toluenesulfonic acid as the dehydrating agent
A method for producing the compound of the formula (1) [Helv. Chim. Acta,7
Two, 996 (1989)].
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記提
案においては反応操作が煩雑であり、また収率が低い等
の問題点を有しており、必ずしも満足できるものではな
かった。However, in the above proposal, the reaction operation is complicated, and there are problems such as a low yield, and it is not always satisfactory.
【０００６】[0006]
【課題を解決するための手段】そこで、本発明者らは、
上述の問題点を解決するため鋭意研究を行ってきた。そ
の結果、後記式（２）の脱水環化剤としてハロゲン化亜
鉛を選ぶことにより、反応操作が極めて簡便で副生成物
を伴うなうことなく、定量的に式（１）の化合物を合成
できることを発見して本発明を完成した。従って、本発
明の目的は、高収率、高純度に式（１）の化合物を製造
できる工業的に有利な新規製法を提供するにある。Means for Solving the Problems Accordingly, the present inventors have:
Intensive research has been carried out to solve the above problems. As a result, by selecting zinc halide as the dehydrating cyclizing agent of the formula (2), the reaction operation is extremely simple, and the compound of the formula (1) can be synthesized quantitatively without accompanying by-products. And completed the present invention. Accordingly, an object of the present invention is to provide a novel industrially advantageous production method capable of producing the compound of the formula (1) in high yield and high purity.
【０００７】本発明によれば、後記式（２）で表される
（−）−８α，１３−ジヒドロキシ−１４，１５，１６
−トリノルラブダンを有機溶媒中、ハロゲン化亜鉛と接
触環化反応させることにより、前記式（１）で表される
（−）−８α，１３−エポキシ−１４，１５，１６−ト
リノルラブダンを容易に製造することができる。According to the present invention, (-)-8α, 13-dihydroxy-14,15,16 represented by the following formula (2)
-Trinorlavdane is subjected to a catalytic cyclization reaction with zinc halide in an organic solvent to give (-)-8α, 13-epoxy-14,15,16-trinorlavyl represented by the above formula (1). Dan can be easily manufactured.
【０００８】本発明の式（１）の化合物を合成する上記
の反応を反応式で示すと、以下のように表すことができ
る。The above reaction for synthesizing the compound of the formula (1) of the present invention can be represented by the following reaction scheme.
【化４】 但し、Ｘはハロゲン原子を示す、Embedded image X represents a halogen atom,
【０００９】上記反応式に従って、式（１）の化合物の
製造法について更に具体的に説明する。式（１）化合物
合成の出発原料である式（２）の化合物は、例えば前記
した従来提案の方法により容易に合成することができる
[Helv.Chim.Acta,63,1932(1980)]）。該提案によれば、
市場で容易に入手できるマノールから製造できるアンブ
レイノリドを水素化リチウムアルミニウムで還元するこ
とにより、式（２）の化合物を高収率、高純度に製造す
ることができる。The method for producing the compound of the formula (1) will be described more specifically according to the above reaction formula. The compound of the formula (2), which is a starting material for the synthesis of the compound of the formula (1), can be easily synthesized, for example, by the above-mentioned conventionally proposed method.
[Helv. Chim. Acta, 63 , 1932 (1980)]. According to the proposal,
By reducing amblenolide, which can be produced from manol, which is easily available on the market, with lithium aluminum hydride, the compound of formula (2) can be produced in high yield and high purity.
【００１０】上記反応式において、式（１）の化合物を
合成するには、式（２）の化合物を有機溶媒中、ハロゲ
ン化亜鉛と接触環化反応させることにより、容易に行う
ことができる。In the above reaction scheme, the compound of the formula (1) can be easily synthesized by subjecting the compound of the formula (2) to a catalytic cyclization reaction with a zinc halide in an organic solvent.
【００１１】この反応の反応温度および反応時間は、例
えば約−２０℃〜約１００℃程度、より好ましくは約０
℃〜約５０℃の温度範囲で、約１時間〜約５時間程度を
採用することができる。使用するハロゲン化亜鉛として
は、フッ化亜鉛、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛を例
示でき、好ましくは塩化亜鉛を挙げることができる。ハ
ロゲン化亜鉛の使用量は、式（２）の化合物１モルに対
して、例えば約１モル以上、より好ましくは約１モル〜
約２モル程度の範囲を例示できる。[0011] The reaction temperature and reaction time of this reaction are, for example, about -20 ° C to about 100 ° C, more preferably about 0 ° C.
In a temperature range of from about 0C to about 50C, about 1 hour to about 5 hours can be employed. Examples of the zinc halide used include zinc fluoride, zinc chloride, zinc bromide, and zinc iodide, and preferably zinc chloride. The amount of the zinc halide to be used is, for example, about 1 mol or more, more preferably about 1 mol to 1 mol of the compound of the formula (2).
A range of about 2 mol can be exemplified.
【００１２】また、反応に用いる有機溶媒の種類として
は、例えばジクロルメタン、四塩化炭素、トルエン、ベ
ンゼン、ジエチルエーテル、テトラヒドロフランなどを
示すことができ、これら有機溶媒の使用量は、例えば式
（２）の化合物１重量部に対して約５〜約５０重量部程
度の範囲でよい。The type of the organic solvent used in the reaction includes, for example, dichloromethane, carbon tetrachloride, toluene, benzene, diethyl ether, tetrahydrofuran and the like. In the range of about 5 to about 50 parts by weight per part by weight of the compound.
【００１３】反応終了後、有機溶媒層をデカントして分
離し、アルカリで洗浄後再結晶等により、高収率、高純
度に式（１）の化合物を得ることができる。上述のよう
にして得られる式（１）の化合物は、木様、アンバー様
の香気香味特性を有し、且つ持続性に優れ、食品用並び
に香粧品用調合香料の香料素材として有用である。After completion of the reaction, the organic solvent layer is decanted and separated, washed with an alkali, and recrystallized to obtain the compound of the formula (1) in high yield and high purity. The compound of the formula (1) obtained as described above has woody and amber-like aroma and flavor properties, is excellent in persistence, and is useful as a perfume material for a compounded perfume for foods and cosmetics.
【００１４】以下に本発明について、実施例を挙げて更
に詳細に説明する。Now, the present invention will be described in further detail with reference to Examples.
実施例１ （−）−８α，１３−エポキシ−１４，１
５，１６−トリノルラブダンの合成［式（１）の化合
物］。Example 1 (-)-8α, 13-epoxy-14,1
Synthesis of 5,16-trinorrabane [compound of formula (1)].
【００１５】塩化亜鉛１．０ｇ（７．３ミリモル）と塩
化メチレン１０ｇをフラスコに仕込み、室温下に撹拌し
ながら（−）−８α，１３−ジヒドロキシ−１４，１
５，１６−トリノルラブダン１．０ｇ（３．７ミリモ
ル）を滴下する。滴下後、更に同温度で３時間撹拌し、
反応させる。A flask was charged with 1.0 g (7.3 mmol) of zinc chloride and 10 g of methylene chloride, and stirred at room temperature with (-)-8α, 13-dihydroxy-14,1.
1.0 g (3.7 mmol) of 5,16-trinorrabane are added dropwise. After dropping, the mixture is further stirred at the same temperature for 3 hours,
Let react.
【００１６】反応終了後、デカントして得た塩化メチレ
ン層を炭酸水素ナトリウム水溶液洗浄、硫酸ナトリウム
で乾燥した後、塩化メチレンを回収して粗製物０．９ｇ
を得た。得られた粗製物を９５％エタノールで再結晶す
ることにより、純粋な式（１）の化合物０．８ｇを得
た。 収率：８５％ 融点：７８．４℃ 施光度［α］20 D：−１２．９°（Ｃ＝１．１０，ＣＨ
Ｃｌ3）After completion of the reaction, the methylene chloride layer obtained by decanting was washed with an aqueous sodium hydrogen carbonate solution and dried over sodium sulfate, and then methylene chloride was recovered to obtain 0.9 g of a crude product.
I got The obtained crude product was recrystallized from 95% ethanol to obtain 0.8 g of a pure compound of the formula (1). Yield: 85% Melting point: 78.4 ° C. Light intensity [α] 20 D : −12.9 ° (C = 1.10, CH
Cl 3 )
【００１７】[0017]
【発明の効果】アンバー様などの香気香味を有し、香粧
品用あるいは食品用の調合香料素材として従来から利用
されてきた（−）−８α，１３−エポキシ−１４，１
５，１６−トリノルラブダンの新規製法を提供できる。
この製法によると、（−）−８α，１３−ジヒドロキシ
−１４，１５，１６−トリノルラブダンを有機溶媒中、
ハロゲン化亜鉛と接触環化させる、わずか１工程反応で
目的化合物を高収率、高純度に得ることができる。EFFECT OF THE INVENTION (-)-8α, 13-epoxy-14,1 which has an amber-like flavor and has been conventionally used as a compounded flavor material for cosmetics or foods.
A new method for producing 5,16-trinorraband can be provided.
According to this production method, (-)-8α, 13-dihydroxy-14,15,16-trinorrabane is dissolved in an organic solvent,
The target compound can be obtained in high yield and high purity by only one step reaction in which the catalyst is cyclized with zinc halide.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C07D 311/00 C07D 307/00 C11B 9/00 A61K 7/46 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C07D 311/00 C07D 307/00 C11B 9/00 A61K 7/46 CA (STN) REGISTRY (STN)
Claims (1)
１５，１６−トリノルラブダンを有機溶媒中、ハロゲン
化亜鉛と接触させて環化反応させることを特徴とする下
記式（１） 【化２】 で表される（−）−８α，１３−エポキシ−１４，１
５，１６−トリノルラブダンの製法。(1) The following formula (2): (-)-8α, 13-dihydroxy-14 represented by
The following cyclization reaction is carried out by bringing 15,16-trinorrabandane into contact with zinc halide in an organic solvent to cause a cyclization reaction. (-)-8α, 13-epoxy-14,1 represented by
Manufacturing method of 5,16-trinorrabandan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25732094A JP3247258B2 (en) | 1994-09-28 | 1994-09-28 | Production method of (-)-8α, 13-epoxy-14,15,16-trinorrabane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25732094A JP3247258B2 (en) | 1994-09-28 | 1994-09-28 | Production method of (-)-8α, 13-epoxy-14,15,16-trinorrabane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0892237A JPH0892237A (en) | 1996-04-09 |
| JP3247258B2 true JP3247258B2 (en) | 2002-01-15 |
Family
ID=17304729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25732094A Expired - Fee Related JP3247258B2 (en) | 1994-09-28 | 1994-09-28 | Production method of (-)-8α, 13-epoxy-14,15,16-trinorrabane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3247258B2 (en) |
-
1994
- 1994-09-28 JP JP25732094A patent/JP3247258B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| Ｈｅｌｖｅｔｉｃａ Ｃｈｉｍｉｃａ Ａｃｔａ，Ｖｏｌ．６９（１９８６），ｐａｇｅｓ１６３−１７３ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0892237A (en) | 1996-04-09 |
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