JPH07109270A - Production of (-)-8alpha,13-epoxy-14,15,16trinorlabda-12-ene and novel intermediate thereof - Google Patents
Production of (-)-8alpha,13-epoxy-14,15,16trinorlabda-12-ene and novel intermediate thereofInfo
- Publication number
- JPH07109270A JPH07109270A JP5276246A JP27624693A JPH07109270A JP H07109270 A JPH07109270 A JP H07109270A JP 5276246 A JP5276246 A JP 5276246A JP 27624693 A JP27624693 A JP 27624693A JP H07109270 A JPH07109270 A JP H07109270A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- hydroxy
- epoxy
- trinorlabda
- 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.)
- Granted
Links
Landscapes
- Pyrane Compounds (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
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 has the following formula (1), which has a fragrant flavor such as wood and amber, and has been conventionally used as a blended fragrance material for cosmetics or foods.
【０００２】[0002]
【化６】 [Chemical 6]
【０００３】で表される（−）−８α，１３−エポキシ
−１４，１５，１６−トリノルラブダ−１２−エンの製
法および該化合物の合成中間体として有用でそれ自体、
木様、アンバー様の香気香味を有し、調合香料素材とし
て利用できる新規な下記式（２）A process for producing (-)-8α, 13-epoxy-14,15,16-trinorlabda-12-ene represented by and useful as a synthetic intermediate for the compound itself,
A novel formula (2) having a woody, amber-like aroma and can be used as a blended flavoring material
【０００４】[0004]
【化７】 [Chemical 7]
【０００５】［式中、波線はシスまたはトランス異性体
を示し、Ｒはメチル基またはエチル基を示す］で表され
る光学活性な８α−ヒドロキシ−１３−アルコキシ−１
４，１５，１６−トリノルラブダ−１２−エン類に関す
る。An optically active 8α-hydroxy-13-alkoxy-1 represented by the formula: wherein the wavy line represents a cis or trans isomer and R represents a methyl group or an ethyl group.
It relates to 4,15,16-trinorlabda-12-enes.
【０００６】[0006]
【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、光学
活性な８α，１３−エポキシ−１４，１５，１６−トリ
ノルラブダ−１３−オン（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して光学活性な８α，１３
−ジヒドロキシ−１４，１５，１６−トリノルラブダン
とし、次に三酸化クロムで酸化して光学活性な１３−ヒ
ドロキシ−８α，１３−エポキシ−１４，１５，１６−
トリノルラブダンを得、更にそれを蒸留することによ
り、３工程で式（１）化合物を合成する方法が提案され
ている[Agr.Biol.Chem.,30(7),659■662,1966]。2. Description of the Related Art Heretofore, some reports have been made on a method for producing the compound of the formula (1). For example, an optically active 8α, 13-epoxy-14,15,16-trinorlabda-13-one (ambreinolide) is reduced with lithium aluminum hydride to obtain an optically active 8α, 13.
-Dihydroxy-14,15,16-trinorlabdane and then oxidized with chromium trioxide to give optically active 13-hydroxy-8α, 13-epoxy-14,15,16-
A method of synthesizing the compound of formula (1) in three steps by obtaining trinorlabdane and further distilling it has been proposed [Agr. Biol. Chem., 30 (7), 659 ■ 662, 1966. ].
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、上記提
案における出発原料であるアンブレイノリドは、マノー
ルからの製造では多工程且つ低収率であり、あるいはフ
ァルネシル酢酸の閉環法においては光学分割をしなけれ
ばならず、工業的に有利な製造法とは言えるものではな
く、解決すべき課題があった［アンブレイノリドの合成
法については、Helv.Chim.Acta.,35,817■824,1952;Ag
r.Biol.Chem.,54(2),571■573,1990参照］。However, ambreinolide, which is the starting material in the above proposal, has many steps and low yield in the production from manol, or it must be optically resolved in the ring closure method of farnesyl acetic acid. However, it was not an industrially advantageous manufacturing method, and there was a problem to be solved [For the method of synthesizing ambreinolide, see Helv.Chim.Acta., 35,817 ■ 824,1952; Ag.
r. Biol. Chem., 54 (2), 571 ■ 573, 1990].
【０００８】[0008]
【課題を解決するための手段】そこで、本発明者らは、
アンブレイノリドを経由しないで香料として有用な上記
式（１）の化合物を工業的に有利に合成できる製造法を
確立するため鋭意研究を行ってきた。その結果、市場で
容易に入手することができるスクラレオリドを還元して
得られる式（３）の化合物を出発原料に選ぶことによ
り、わずか２工程で式（１）の化合物を合成できるこ
と、更に式（１）の化合物の合成中間体である式（２）
の化合物が従来文献未記載であり、それ自体、木様、ア
ンバー様の香気香味を有し、且つ持続性に優れ、調合香
料素材として有用であることを発見して本発明を完成し
た。Therefore, the present inventors have
The inventors have earnestly studied to establish a production method capable of industrially advantageously synthesizing the compound of the above formula (1) useful as a fragrance without passing through ambreinolide. As a result, the compound of formula (1) can be synthesized in only two steps by selecting the compound of formula (3) obtained by reducing sclareolide, which can be easily obtained on the market, as a starting material, Formula (2) which is a synthetic intermediate of the compound of 1)
The present invention has been completed by discovering that the compound of (1) has not been described in the conventional literature, has a wood-like or amber-like fragrance per se, is excellent in sustainability, and is useful as a blended fragrance material.
【０００９】従って本発明の目的は、式（１）の化合物
を工業的に有利に製造できる方法を提供するにある。ま
た、本発明の他の目的は、従来文献に未記載の式（２）
の化合物を提供するにある。以下、本発明を詳細に説明
する。Therefore, it is an object of the present invention to provide a method by which a compound of formula (1) can be produced industrially advantageously. Another object of the present invention is to provide a formula (2) not described in the prior art document.
To provide the compound of Hereinafter, the present invention will be described in detail.
【００１０】本発明によれば、下記式（３）According to the present invention, the following formula (3)
【００１１】[0011]
【化８】 [Chemical 8]
【００１２】［式中、波線はシスまたはトランス異性体
を示す］で表される光学活性な１２−ヒドロキシ−８
α，１２−エポキシ−１３，１４，１５，１６−テトラ
ノルラブダンを有機溶媒中、塩基の存在下に下記式
（４）An optically active 12-hydroxy-8 represented by the formula: wherein the wavy line represents a cis or trans isomer.
α, 12-epoxy-13,14,15,16-tetranorlabdane in the following formula (4) in the presence of a base in an organic solvent.
【００１３】[0013]
【化９】 [Chemical 9]
【００１４】［式中、Ｒはメチル基またはエチル基を示
し、Ｐｈはフェニル基を示し、Ｘはハロゲン原子を示
す］で表されるウイテッヒ試薬と反応させて下記式
（２）[Wherein R represents a methyl group or an ethyl group, Ph represents a phenyl group, and X represents a halogen atom], and the compound is reacted with a Wittig reagent represented by the following formula (2):
【００１５】[0015]
【化１０】 [Chemical 10]
【００１６】［式中、波線はシスまたはトランス異性体
を示し、Ｒはメチル基またはエチル基を示す］で表され
る光学活性８α−ヒドロキシ−１３−アルコキシ−１
４，１５，１６−トリノルラブダ−１２−エン類を形成
させ、該式（２）の化合物を酸の存在下に加熱閉環反応
させることにより上記式（１）で表される（−）−８
α，１３−エポキシ−１４，１５，１６−トリノルラブ
ダ−１２−エンが容易に製造される。Optically active 8α-hydroxy-13-alkoxy-1 represented by the formula: wherein the wavy line represents a cis or trans isomer and R represents a methyl group or an ethyl group.
4,15,16-trinorlabda-12-enes are formed, and the compound of the formula (2) is subjected to a ring closure reaction by heating in the presence of an acid, and (-)-8 represented by the above formula (1).
The α, 13-epoxy-14,15,16-trinorlabda-12-ene is easily prepared.
【００１７】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 formula.
【００１８】[0018]
【化１１】 [Chemical 11]
【００１９】［式中、波線はシスまたはトランス異性体
を示し、Ｒはメチル基またはエチル基を示し、Ｐｈはフ
ェニル基を示し、Ｘはハロゲン原子を示す、］[In the formula, wavy lines represent cis or trans isomers, R represents a methyl group or an ethyl group, Ph represents a phenyl group, and X represents a halogen atom.]
【００２０】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。The method for producing the compound of formula (1) will be described more specifically according to the above reaction scheme.
【００２１】式（１）化合物合成の出発原料である式
（３）の化合物は、市場で入手容易なスクラレオリドを
還元する従来提案の方法により容易に合成することがで
きる（ＵＳＰ４８７２９１７号参照）。The compound of formula (3), which is the starting material for synthesizing the compound of formula (1), can be easily synthesized by a conventionally proposed method of reducing sclareolide, which is easily available on the market (see US Pat. No. 4,872,917).
【００２２】上記反応式において、式（２）の化合物を
合成するには、式（３）の化合物を有機溶媒中、塩基の
存在下に式（４）の化合物と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 formula (2) is easily synthesized by reacting the compound of formula (3) with the compound of formula (4) in the presence of a base in an organic solvent. be able to.
【００２３】この反応の反応温度および反応時間は、例
えば約−６０℃〜約１５０℃程度、より好ましくは約０
℃〜約５０℃の温度範囲で、約２時間〜約５０時間程度
を採用できる。使用する式（４）のウイテッヒ試薬の具
体例としては、例えばメトキシメチルトリフェニルホス
ホニウムクロリド［ＣＨ3ＯＣＨ2Ｐ（Ｃ6Ｈ5）3Ｃ
ｌ］、エトキシメチルトリフェニルホスホニウムブロリ
ド［ＣＨ3ＣＨ2ＯＣＨ2Ｐ（Ｃ6Ｈ5）3Ｂｒ］などを挙げ
ることができる。式（４）の化合物の使用量は、式
（３）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２モル〜約３モル程度の範囲を例示で
きる。また、反応に用いる塩基の種類としては、例えば
ブチルリチウム、水素化ナトリウム、ナトリウムアミ
ド、ナトリウムメトキシド等を挙げることができ、その
使用量は式（４）の化合物１モルに対して、約１モル〜
約１．５モル程度を採用することができる。更に、有機
溶媒の種類としては、例えばエチルエーテル、テトラヒ
ドロフラン、ジメチルスルホキシド、ジメチルホルムア
ミド、ジメトキシエタ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（３）の化合物１重量部
に対して約２〜約１０重量部程度の範囲でよい。The reaction temperature and reaction time of this reaction are, for example, about -60 ° C to about 150 ° C, more preferably about 0 ° C.
In the temperature range of ℃ to about 50 ℃, about 2 hours to about 50 hours can be adopted. Specific examples of the Wittig reagent of the formula (4) to be used include, for example, methoxymethyltriphenylphosphonium chloride [CH 3 OCH 2 P (C 6 H 5 ) 3 C
1], ethoxymethyltriphenylphosphonium bromide [CH 3 CH 2 OCH 2 P (C 6 H 5 ) 3 Br], and the like. The amount of the compound of the formula (4) used is, for example, about 1 mol or more relative to 1 mol of the compound of the formula (3),
More preferably, the range of about 2 mol to about 3 mol can be exemplified. Examples of the type of base used in the reaction include butyllithium, sodium hydride, sodium amide, sodium methoxide and the like, and the amount thereof used is about 1 with respect to 1 mol of the compound of the formula (4). Mol ~
About 1.5 mol can be adopted. Further, as the kind of the organic solvent, for example, ethyl ether, tetrahydrofuran, dimethylsulfoxide, dimethylformamide, dimethoxyethane, etc. can be shown. The amount of these organic solvents used is, for example, 1 part by weight of the compound of the formula (3). And about 2 to about 10 parts by weight.
【００２４】反応終了後、生成物を洗浄、抽出、乾燥、
蒸留、カラムクロマトグラフィーなどの通常の分離手段
を適宜に採用して好収率、好純度に式（２）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（２）
は、シスおよびトランス異性体のほぼ等量混合物であ
る。これら異性体は、式（２）の化合物をカラムクロマ
トグラフィーなどの分離手段を適宜に用いることによ
り、単離することができる。このようにして単離した異
性体並びに該異性体の混合物は、いずれも木様、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 product is washed, extracted, dried,
The compound of formula (2) can be obtained in good yield and good purity by appropriately adopting ordinary separation means such as distillation and column chromatography. Equation (2) obtained as described above
Is a nearly equal mixture of cis and trans isomers. These isomers can be isolated by appropriately using a separation means such as column chromatography for the compound of formula (2). The isomers thus isolated and the mixture of the isomers each have a wood-like and amber-like aroma and flavor characteristic and are excellent in sustainability, and are used as a perfume material for a compounded perfume for foods and cosmetics. It is useful.
【００２５】式（２）の化合物の具体例としては、光学
活性な１２−トランス又は１２−シスの８α−ヒドロキ
シ−１３−メトキシ−１４，１５，１６−トリノルラブ
ダ−１２−エン（沸点：１４５〜１５０℃／０．３ｍｍ
Ｈｇ）及び１２−トランス又は１２−シスの８α−ヒド
ロキシ−１３−エトキシ−１４，１５，１６−トリノル
ラブダ−１２−エン（沸点：１４８〜１５４℃／０．３
ｍｍＨｇ）を挙げることができる。Specific examples of the compound of the formula (2) include optically active 12-trans or 12-cis 8α-hydroxy-13-methoxy-14,15,16-trinorlabda-12-ene (boiling point: 145 to 145). 150 ° C / 0.3mm
Hg) and 12-trans or 12-cis 8α-hydroxy-13-ethoxy-14,15,16-trinorlabda-12-ene (boiling point: 148 to 154 ° C / 0.3).
mmHg) can be mentioned.
【００２６】上記反応式において、式（２）の化合物か
ら式（１）の化合物を合成するには、式（２）の化合物
を酸触媒の存在下に加熱閉環反応させることにより容易
に実施できる。この反応の反応温度は、例えば約５０℃
〜約２００℃程度、より好ましくは約１００℃〜約１５
０℃程度の温度範囲で行うことができる。反応時間は反
応温度により異なるが、通常、約０．５時間〜約２時間
程度でよい。この反応に用いる酸触媒の種類としては、
例えばｐ−トルエンスルホン酸、硫酸水素カリウム、硫
酸水素ナトリウム、塩酸、硫酸、三フッ化ホウ素エーテ
ル錯体、四塩化スズなどを挙げることができ、その使用
量は、例えば式（２）の化合物１重量部に対して約０．
００１〜約０．１重量部程度を例示できる。In the above reaction scheme, the compound of formula (1) can be easily synthesized from the compound of formula (2) by subjecting the compound of formula (2) to a heat ring closure reaction in the presence of an acid catalyst. . The reaction temperature of this reaction is, for example, about 50 ° C.
To about 200 ° C., more preferably about 100 ° C. to about 15
It can be performed in a temperature range of about 0 ° C. The reaction time varies depending on the reaction temperature, but is usually about 0.5 hour to about 2 hours. The type of acid catalyst used in this reaction is
For example, p-toluenesulfonic acid, potassium hydrogensulfate, sodium hydrogensulfate, hydrochloric acid, sulfuric acid, boron trifluoride ether complex, tin tetrachloride and the like can be mentioned, and the amount thereof is, for example, 1 weight of the compound of the formula (2). About 0.
001 to about 0.1 part by weight can be exemplified.
【００２７】この反応は、反応容器に式（２）の化合物
及び酸触媒を仕込み、加熱接触させて行うこともできる
が、通常は式（２）の化合物及び酸触媒の混合物を蒸留
することにより、容易に行うことができる。反応終了後
は通常の分離・精製手段、例えば蒸留、洗浄、抽出、乾
燥、カラムクロマトグラフィーなどの処理を適宜に採用
して好収率・好純度に式（１）の（−）−８α，１３−
エポキシ−１４，１５，１６−トリノルラブダ−１２−
エンを得ることができる。This reaction can be carried out by charging the compound of the formula (2) and the acid catalyst into a reaction vessel and bringing them into contact with each other by heating. Usually, a mixture of the compound of the formula (2) and the acid catalyst is distilled. , Can be done easily. After completion of the reaction, usual separation / purification means such as distillation, washing, extraction, drying, and column chromatography are appropriately adopted to obtain good yield and good purity in (-)-8α of the formula (1), 13-
Epoxy-14,15,16-trinorlabda-12-
You can get en.
【００２８】以下に本発明について、実施例及び参考例
を挙げて更に詳細に説明する。The present invention will be described in more detail below with reference to examples and reference examples.
【００２９】[0029]
【実施例１】 光学活性８α−ヒドロキシ−１３−メト
キシ−１４，１５，１６−トリノルラブダ−１２−エン
の合成［式（２）の化合物］。Example 1 Synthesis of optically active 8α-hydroxy-13-methoxy-14,15,16-trinorlabda-12-ene [compound of formula (2)].
【００３０】水素化ナトリウム（純度６０％）２．２ｇ
（５５ミリモル）をフラスコに仕込み、ヘキサンで洗浄
して鉱油を除去した。次にジメチルスルホキシド（以
下、ＤＭＳＯという）１００ｍｌをフラスコに仕込み、
６０℃で２時間撹拌した。室温まで冷却した後、メトキ
シメチルトリフェニルホスホニウムクロリド１８．９ｇ
（５５ミリモル）を加え、同温度で３０分間撹拌した。
次に光学活性１２−ヒドロキシ−８α，１２−エポキシ
−１３，１４，１５，１６−テトラノルラブダン６．３
ｇ（２５ミリモル）のＤＭＳＯ２５ｍｌ溶液を室温下で
加え、５０℃まで加熱して２０時間撹拌した。冷却後、
水を加え、エーテルで３回抽出した。エーテル層は食塩
水で洗浄後、無水硫酸ナトリウムで脱水した。エーテル
回収後、得られた粗製物１７．２ｇをシリカゲルカラム
クロマトグラフィー（ヘキサン：エーテル＝１：１）で
処理して、シスおよびトランス異性体のほぼ等量混合物
である純粋な式（２）の化合物５．０ｇ（収率：７１
％）を得た。以下にＩＲおよびＮＭＲのデータを記載す
る。2.2 g of sodium hydride (purity 60%)
(55 mmol) was charged into a flask and washed with hexane to remove mineral oil. Next, 100 ml of dimethyl sulfoxide (hereinafter referred to as DMSO) was charged into the flask,
The mixture was stirred at 60 ° C for 2 hours. After cooling to room temperature, 18.9 g of methoxymethyltriphenylphosphonium chloride
(55 mmol) was added, and the mixture was stirred at the same temperature for 30 minutes.
Next, optically active 12-hydroxy-8α, 12-epoxy-13,14,15,16-tetranorlabdane 6.3
A solution of g (25 mmol) in DMSO (25 ml) was added at room temperature, and the mixture was heated to 50 ° C. and stirred for 20 hours. After cooling
Water was added, and the mixture was extracted 3 times with ether. The ether layer was washed with brine and then dehydrated with anhydrous sodium sulfate. After recovery of ether, 17.2 g of the obtained crude product was treated with silica gel column chromatography (hexane: ether = 1: 1) to obtain a pure compound of formula (2) which was a mixture of almost equal amounts of cis and trans isomers. 5.0 g of compound (yield: 71
%) Was obtained. The IR and NMR data are described below.
【００３１】IR 3420,1657,1462,1388,1209,1108,938c
m-1 NMR1 H(CDcl3) δ=0.80(S,12H),0.87(S,6H),1.18(S,6H),
0.9■2.5(m,30H),3.48(S ,3H),3.60
(S,3H),4.4■5.0(m,2H),5.8(d,1H),6.3(d,1H)13 C(CDcl3) δ=15.18,15.29,18.59,19.35,20.27,21.5
7,23.14,24.33,33.27,3 3.49,38.85,3
9.02,39.94,40.10,41.92,43.41,44.16,55.92,56
.14,59.49,62.47,62.80,73.85,74.45,105.9
8,109.71,145.20, 146.82IR 3420,1657,1462,1388,1209,1108,938c
m- 1 NMR 1 H (CDcl 3 ) δ = 0.80 (S, 12H), 0.87 (S, 6H), 1.18 (S, 6H),
0.9 ■ 2.5 (m, 30H), 3.48 (S, 3H), 3.60
(S, 3H), 4.4 ■ 5.0 (m, 2H), 5.8 (d, 1H), 6.3 (d, 1H) 13 C (CDcl 3 ) δ = 15.18,15.29,18.59,19.35,20.27,21.5
7,23.14,24.33,33.27,3 3.49,38.85,3
9.02,39.94,40.10,41.92,43.41,44.16,55.92,56
.14,59.49,62.47,62.80,73.85,74.45,105.9
8,109.71,145.20, 146.82
【００３２】[0032]
【実施例２】 （−）−８α，１３−エポキシ−１４，
１５，１６−トリノルラブダ−１２−エンの合成［式
（１）の化合物］。蒸留塔に式（２）の化合物１．００
ｇ及び０．０１ｇの硫酸水素カリウムを仕込み、減圧下
に蒸留することにより、純粋な式（１）の化合物０．８
０ｇを得た（沸点：１２５℃〜１２７℃／０．３ｍｍＨ
ｇ、収率：９０％）。Example 2 (−)-8α, 13-epoxy-14,14
Synthesis of 15,16-trinorlabda-12-ene [compound of formula (1)]. The compound of formula (2) 1.00 in the distillation column
g and 0.01 g of potassium hydrogensulfate were charged and distilled under reduced pressure to give pure compound of formula (1) 0.8
0 g was obtained (boiling point: 125 ° C. to 127 ° C./0.3 mmH
g, yield: 90%).
【００３３】 留出物 温度／減圧度 留出量 式（１）化合物 〜１２７℃／０．３ｍｍＨｇ ０．８０ｇ 残渣 ０．１０ｇDistillate Temperature / Decompression degree Distillation amount Formula (1) compound to 127 ° C./0.3 mmHg 0.80 g Residue 0.10 g
【００３４】[0034]
【参考例１】 リラタイプの調合香料組成物として下記
の各成分（重量部）を混合した。 [Reference Example 1] The following components (parts by weight) were mixed as a lira-type compounded fragrance composition.
【００３５】上記組成物９７ｇに光学活性８α−ヒドロ
キシ−１３−メトキシ−１４，１５，１６−トリノルラ
ブダ−１２−エンを３ｇ混合して新規調合香料組成物を
調製した。この新規調合香料組成物と該化合物を加えて
いない上記のリラタイプの調合香料組成物について、専
門パネラー１０人により比較した。その結果、専門パネ
ラー１０人の全員が該化合物を加えた新規調合香料組成
物は、ナチュラル感のあるフレッシュな中にも甘さを伴
ったウッディー調（木様）の特性が強調され、天然のリ
ラの特徴をとらえ持続性の点でも格段に優れているとし
た。A novel compounded fragrance composition was prepared by mixing 97 g of the above composition with 3 g of optically active 8α-hydroxy-13-methoxy-14,15,16-trinorlabda-12-ene. This newly prepared fragrance composition and the above-mentioned lyre-type fragrance composition containing no compound were compared by 10 expert panelists. As a result, the new compounded fragrance composition in which all 10 professional panelists added the compound emphasized the woody (woody) characteristic with sweetness even though it was fresh with a natural feel It was noted that it was extremely superior in terms of sustainability by capturing the characteristics of the lira.
【００３６】上述の専門パネラーによる官能検査におい
て、光学活性８α−ヒドロキシ−１３−メトキシ−１
４，１５，１６−トリノルラブダ−１２−エンの代わり
に光学活性８α−ヒドロキシ−１３−エトキシ−１４，
１５，１６−トリノルラブダ−１２−エンを４ｇ混合し
て新規調合香料組成物を調製した。この新規調合香料組
成物と該化合物を加えていない上記のリラタイプの調合
香料組成物について、専門パネラー１０人により比較し
た。その結果、専門パネラー１０人の全員が該化合物を
加えた新規調合香料組成物は、ナチュラル感のあるフレ
ッシュな中にも甘さを伴ったウッディー調（木様）の特
性が強調され、天然のリラの特徴をとらえ持続性の点で
も格段に優れているとした。In the sensory test by the above-mentioned professional panelist, optically active 8α-hydroxy-13-methoxy-1
Optically active 8α-hydroxy-13-ethoxy-14, instead of 4,15,16-trinorlabda-12-ene
A newly prepared fragrance composition was prepared by mixing 4 g of 15,16-trinorlabda-12-ene. This newly prepared fragrance composition and the above-mentioned lyre-type fragrance composition containing no compound were compared by 10 expert panelists. As a result, the new compounded fragrance composition in which all 10 professional panelists added the compound emphasized the woody (woody) characteristic with sweetness even though it was fresh with a natural feel It was noted that it was extremely superior in terms of sustainability by capturing the characteristics of the lira.
【００３７】[0037]
【参考例２】 パイナップル様の調合香料組成物として
下記の各成分（重量）を混合した。 Reference Example 2 The following components (weight) were mixed as a pineapple-like mixed flavor composition.
【００３８】上記組成物９５ｇに光学活性８α−ヒドロ
キシ−１３−エトキシ−１４，１５，１６−トリノルラ
ブダ−１２−エンを５ｇ混合して新規なパイナップル様
の調合香料組成物を調製した。この新規調合香料組成物
と該化合物を加えていない上記のパイナップル様調合香
料組成物について、専門パネラー１０人により比較し
た。その結果、専門パネラー１０人の全員が該化合物を
加えた新規調合香料組成物は、フレッシュなウッディー
調（木様）で甘いパイナップル様の香気が強調された天
然パイナップルの特徴をとらえ持続性の点でも格段に優
れているとした。A novel pineapple-like fragrance composition was prepared by mixing 95 g of the above composition with 5 g of optically active 8α-hydroxy-13-ethoxy-14,15,16-trinorlabda-12-ene. This newly prepared fragrance composition was compared with the above-mentioned pineapple-like prepared fragrance composition in which the compound was not added, by 10 expert panelists. As a result, the new compounded fragrance composition in which all of the 10 professional panelists added the compound caught the characteristic of natural pineapple in which the fresh woody (woody) and sweet pineapple-like aroma was emphasized, and the durability was maintained. However, he said that he was significantly better.
【００３９】上述の専門パネラーによる官能検査におい
て、光学活性８α−ヒドロキシ−１３−エトキシ−１
４，１５，１６−トリノルラブダ−１２−エンの代わり
に光学活性８α−ヒドロキシ−１３−メトキシ−１４，
１５，１６−トリノルラブダ−１２−エンを４ｇ混合し
て新規調合香料組成物を調製した。この新規調合香料組
成物と該化合物を加えていない上記のパイナップル様調
合香料組成物について、専門パネラー１０人により比較
した。その結果、専門パネラー１０人の全員が該化合物
を加えた新規調合香料組成物は、フレッシュなウッディ
ー調（木様）で甘いパイナップル様の香気が強調された
天然パイナップルの特徴をとらえ持続性の点でも格段に
優れているとした。In the sensory test by the above-mentioned specialized panelist, optically active 8α-hydroxy-13-ethoxy-1
Instead of 4,15,16-trinorlabda-12-ene, optically active 8α-hydroxy-13-methoxy-14,14
A newly prepared fragrance composition was prepared by mixing 4 g of 15,16-trinorlabda-12-ene. This newly prepared fragrance composition was compared with the above-mentioned pineapple-like prepared fragrance composition in which the compound was not added, by 10 expert panelists. As a result, the new compounded fragrance composition in which all of the 10 professional panelists added the compound caught the characteristic of natural pineapple in which the fresh woody (woody) and sweet pineapple-like aroma was emphasized, and the durability was maintained. However, he said that he was significantly better.
【００４０】[0040]
【発明の効果】本発明によれば、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−１４，１５，１６−トリノルラブダ−１２−エン
の製法ならびに該化合物の合成中間体として有用でそれ
自体、木様、アンバー様の香気香味を有し、調合香料素
材として利用できる新規な光学活性な８α−ヒドロキシ
−１３−アルコキシ−１４，１５，１６−トリノルラブ
ダ−１２−エン類が提供される。該製法は、わずか１工
程で式（１）の化合物を好収率・好純度に合成できる。EFFECTS OF THE INVENTION According to the present invention, (-)-8α, 13-epoxy-14, which has an aroma like amber and has been conventionally used as a blended perfume material for cosmetics or foods. A novel optically active 8α-hydroxy compound which is useful as a process for producing 15,16-trinorlabda-12-ene and as a synthetic intermediate for the compound, and has a wood-like and amber-like aroma and flavor and can be used as a raw material for a prepared perfume. -13-Alkoxy-14,15,16-trinorlabda-12-enes are provided. According to this production method, the compound of formula (1) can be synthesized in good yield and good purity in only one step.
Claims (2)
される光学活性な１２−ヒドロキシ−８α，１２−エポ
キシ−１３，１４，１５，１６−テトラノルラブダンを
有機溶媒中、塩基の存在下に下記式（４） 【化２】 ［式中、Ｒはメチル基またはエチル基を示し、Ｐｈはフ
ェニル基を示し、Ｘはハロゲン原子を示す］で表される
ウイテッヒ試薬と反応させて下記式（２） 【化３】 ［式中、波線はシスまたはトランス異性体を示し、Ｒは
メチル基またはエチル基を示す］で表される光学活性な
８α−ヒドロキシ−１３−アルコキシ−１４，１５，１
６−トリノルラブダ−１２−エン類を形成させ、該式
（２）の化合物を酸の存在下に加熱閉環反応させること
を特徴とする下記式（１） 【化４】 で表される（−）−８α，１３−エポキシ−１４，１
５，１６−トリノルラブダ−１２−エンの製法。1. The following formula (3): [Wherein the wavy line represents a cis or trans isomer] and an optically active 12-hydroxy-8α, 12-epoxy-13,14,15,16-tetranorlabdane of an organic solvent In the presence of the following formula (4): [Wherein, R represents a methyl group or an ethyl group, Ph represents a phenyl group, and X represents a halogen atom], and reacted with a Wittig reagent represented by the following formula (2): [In the formula, the wavy line represents a cis or trans isomer, and R represents a methyl group or an ethyl group.] Optically active 8α-hydroxy-13-alkoxy-14,15,1
6-trinorlabda-12-ene is formed, and the compound of the formula (2) is subjected to a ring closure reaction by heating in the presence of an acid, and the following formula (1): (-)-8α, 13-epoxy-14,1 represented by
A method for producing 5,16-trinorlabda-12-ene.
メチル基またはエチル基を示す］で表される光学活性な
８α−ヒドロキシ−１３−アルコキシ−１４，１５，１
６−トリノルラブダ−１２−エン類。2. The following formula (2): [In the formula, the wavy line represents a cis or trans isomer, and R represents a methyl group or an ethyl group.] Optically active 8α-hydroxy-13-alkoxy-14,15,1
6-trinorlabda-12-enes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5276246A JP3071621B2 (en) | 1993-10-07 | 1993-10-07 | Process for producing (-)-8α, 13-epoxy-14,15,16-trinorrabuda-12-ene and a novel intermediate thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5276246A JP3071621B2 (en) | 1993-10-07 | 1993-10-07 | Process for producing (-)-8α, 13-epoxy-14,15,16-trinorrabuda-12-ene and a novel intermediate thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07109270A true JPH07109270A (en) | 1995-04-25 |
| JP3071621B2 JP3071621B2 (en) | 2000-07-31 |
Family
ID=17566746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5276246A Expired - Fee Related JP3071621B2 (en) | 1993-10-07 | 1993-10-07 | Process for producing (-)-8α, 13-epoxy-14,15,16-trinorrabuda-12-ene and a novel intermediate thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3071621B2 (en) |
-
1993
- 1993-10-07 JP JP5276246A patent/JP3071621B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3071621B2 (en) | 2000-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3960977A (en) | Process for the preparation of poly-unsaturated hydrocarbons | |
| JP2010506861A (en) | 2,2,3-Trimethylcyclopent-3-enecarbaldehyde derivatives useful as odor substances | |
| US4014951A (en) | Process for the preparation of poly-unsaturated hydrocarbons | |
| JP3071621B2 (en) | Process for producing (-)-8α, 13-epoxy-14,15,16-trinorrabuda-12-ene and a novel intermediate thereof | |
| US4179448A (en) | Spirane derivatives useful as perfuming and flavor-modifying ingredients | |
| US4465618A (en) | Spiranic compound for use as a perfume or flavor-modifying ingredient | |
| KR20100037598A (en) | 6,8,10-undecatrien-(3 or 4)-one and perfume composition | |
| JP4143683B1 (en) | 6,8,10-Undecatrien-3 or 4-ol and perfume composition | |
| JPS6042215B2 (en) | Novel 12-alkoxy-3,7,11-trimethyldodecatetraene | |
| JP4057640B1 (en) | 6,8,10-Undecatrien-4-one and perfume composition | |
| JP5014732B2 (en) | Method for producing anteisoaliphatic aldehyde and perfume composition containing the same | |
| JPH06135878A (en) | 8-hydroxy-8-methylnonanal and fragrance composition containing the same | |
| JP2004161702A (en) | METHOD FOR PRODUCING gamma-JASMOLACTONE | |
| JP2007507563A (en) | Organic compounds | |
| JP6154893B2 (en) | Organic compounds | |
| CH640496A5 (en) | PROCESS FOR THE PREPARATION OF BETA-DAMASCENONE. | |
| JPH0517959B2 (en) | ||
| JP2545289B2 (en) | Method for producing γ-ionones | |
| US4252693A (en) | Perfume compositions containing spirane derivatives | |
| JP2011511813A (en) | Organic compounds | |
| JPS61172839A (en) | 2,5,8-undecatrien-1-ol and ester thereof | |
| JPH1084989A (en) | Production of optically active alpha-ionone | |
| JPH02193989A (en) | Cyclic compound,perfuming or perfumed composition, method of giving,increasing,improving or modifying functionality of perfuming or perfumed product and preparation of perfuming composition and soap,perfumed composition,food and drink and cyclic compound | |
| CN117105755A (en) | Novel method for synthesizing alpha-damascone | |
| JP4358082B2 (en) | PROPANON DERIVATIVE, PROCESS FOR PRODUCING THE SAME AND PERFUME COMPOSITION CONTAINING THE SAME |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |