JPH0694463B2 - Method for producing cyclic terpene compound - Google Patents
Method for producing cyclic terpene compoundInfo
- Publication number
- JPH0694463B2 JPH0694463B2 JP8059589A JP8059589A JPH0694463B2 JP H0694463 B2 JPH0694463 B2 JP H0694463B2 JP 8059589 A JP8059589 A JP 8059589A JP 8059589 A JP8059589 A JP 8059589A JP H0694463 B2 JPH0694463 B2 JP H0694463B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- solution
- nitropropane
- chlorosulfonic acid
- 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.)
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- Pyrane Compounds (AREA)
- Furan Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明により提供される化合物はマッコウ鯨より産し、
貴重な動物性香料として知られる物質又はその合成原料
である。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The compound provided by the present invention is produced from sperm whale,
It is a substance known as a valuable animal fragrance or its synthetic raw material.
従来、下記一般式 （式中、ｎは１もしくは２を表し、ＡはCH2もしくはＣ
＝Ｏを表し、ＲはＡがCH2を表すときは水素原子もしく
は炭素数１〜４のアシル基を表し、ＡがＣ＝Ｏを表すと
きは水素原子もしくは炭素数１〜４のアルキル基を表
す。） で示される化合物（以下化合物（II）と記す）、 又は下記一般式 （式中、ｎおよびＡは式（II）におけるのと同じ意味を
表す。） で示される化合物（以下化合物（III）と記す）から、
下記一般式 （式中、ｎ、ＡおよびＲは式（II）におけるのと同じ意
味を表す。） で示される環状テルペン化合物（以下化合物（Ｉ）と記
す）を製造する方法としては、ニトロプロパン溶媒中−
80〜−85℃の低温下で10培量のフルオロスルホン酸と反
応させる方法が知られている。（Khim.Prir.Soedin1989
in press） 〔発明が解決しようとする課題〕 従来の方法は工業的に実施するには危険で高価なフルオ
ロスルホン酸を大過剰に使用するため、コスト面及び安
全性の面から大きさ欠点がある。Conventionally, the following general formula (In the formula, n represents 1 or 2, A is CH 2 or C
═O, R represents a hydrogen atom or an acyl group having 1 to 4 carbon atoms when A represents CH 2, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms when A represents C═O. Represent ) A compound represented by the following (hereinafter referred to as compound (II)), or (In the formula, n and A have the same meanings as in formula (II).) From the compound (hereinafter referred to as compound (III)),
The following general formula (In the formula, n, A and R have the same meanings as in formula (II).) As a method for producing a cyclic terpene compound (hereinafter referred to as compound (I))
It is known to react with 10 media of fluorosulfonic acid at a low temperature of 80 to -85 ° C. (Khim.Prir.Soedin1989
[Problems to be Solved by the Invention] Since the conventional method uses a large excess of fluorosulfonic acid, which is dangerous and industrially practicable, it has a size defect from the viewpoint of cost and safety. is there.
本発明によれば、化合物（II）もしくは化合物（III）
をクロルスルホン酸と反応させた後、水で処理すること
により、経済的、かつ安全に化合物（Ｉ）を製造するこ
とができる。According to the present invention, compound (II) or compound (III)
Compound (I) can be produced economically and safely by reacting with chlorosulfonic acid and then treating with water.
化合物（Ｉ）、（II）及び（III）において、ＲはＡがC
H2を表すときは水素原子もしくは炭素数１〜４のアシル
基を表し、ＡがＣ＝Ｏを表すときは水素原子もしくは炭
素数１〜４のアルキル基を表す。アシル基の具体例とし
ては、ホルミル基、アセチル基、プロピオニル基及びブ
タノイル基などがある。アルキル基の具体例としては、
メチル基、エチル基、ｎ−プロピル基、イソプロピル
基、ｎ−ブチル基、イソブチル基などがある。In compounds (I), (II) and (III), R is A is C
When H 2 is represented, it represents a hydrogen atom or an acyl group having 1 to 4 carbon atoms, and when A represents C═O, it represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specific examples of the acyl group include a formyl group, an acetyl group, a propionyl group and a butanoyl group. Specific examples of the alkyl group include:
Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group.
本発明において、使用されるクロルスルホン酸の量は化
合物（II）あるいは化合物（III）に対して通常１〜５
培モルである。反応温度は通常−100〜０℃の範囲から
選ばれるが、好ましくは−30〜−80℃である。クロルス
ルホン酸との反応は通常、溶媒の存在下に行われる。用
いられる溶媒は、反応条件下で化合物（II）或いは化合
物（III）と均一に混ざり合い、不活性であれば特に制
限はないが、好ましい溶媒としては、ニトロメタン、ニ
トロプロパンなどのニトロアルカン類、ジクロルメタ
ン、トリクロロエタンなどの塩素化炭化水素、イソプロ
ピルエーテル、テトラヒドロフランなどのエーテル類が
あげられる。クロルスルホン酸との反応の後、水で処理
することにより、化合物（Ｉ）を得ることができる。水
で処理する際の条件は特に制限はないが、発熱による温
度上昇を押さえるために通常、用いたクロルスルホン酸
の５重量培以上の水を用い、０℃付近の温度で処理する
のが好ましい。In the present invention, the amount of chlorosulfonic acid used is usually 1 to 5 with respect to compound (II) or compound (III).
It is a culture mole. The reaction temperature is usually selected in the range of -100 to 0 ° C, preferably -30 to -80 ° C. The reaction with chlorosulfonic acid is usually carried out in the presence of a solvent. The solvent used is not particularly limited as long as it is inactive evenly mixed with the compound (II) or the compound (III) under the reaction conditions and is inert, but preferable solvents include nitroalkanes such as nitromethane and nitropropane, Examples include chlorinated hydrocarbons such as dichloromethane and trichloroethane, and ethers such as isopropyl ether and tetrahydrofuran. Compound (I) can be obtained by treating with water after the reaction with chlorosulfonic acid. The conditions for treatment with water are not particularly limited, but in order to suppress the temperature rise due to heat generation, it is generally preferable to use water of 5 weight% or more of the used chlorosulfonic acid and treat at a temperature near 0 ° C. .
以下に本発明の実施例を示す。Examples of the present invention will be shown below.
実施例１ 4,8,12−トリメチル−3,7,11−トリデカトリエン酸1.2g
の２−ニトロプロパン2ml溶液を窒素雰囲気下におい
て、−70℃に冷却したクロルスルホン酸4.0gの２−ニト
ロプロパン18ml溶液に２分間で滴下した。20分間撹拌
後、反応液を氷50gに注ぎ、エーテル抽出した。エーテ
ル層を重曹水で洗浄した後、硫酸マグネシウムで乾燥
し、溶媒を留去した。得られた油状物質をシリカゲルカ
ラムクロマトグラフィーにより分離し、（±）−ノルア
ンブレノリド（下記構造式）を得た。Example 1 1.2 g of 4,8,12-trimethyl-3,7,11-tridecatrienoic acid
2 ml of 2-nitropropane solution of was added dropwise under nitrogen atmosphere to 18 ml of 2-nitropropane solution of 4.0 g of chlorosulfonic acid cooled to -70 ° C over 2 minutes. After stirring for 20 minutes, the reaction solution was poured into 50 g of ice and extracted with ether. The ether layer was washed with aqueous sodium hydrogen carbonate, dried over magnesium sulfate, and the solvent was evaporated. The obtained oily substance was separated by silica gel column chromatography to obtain (±) -noramblenolide (the following structural formula).
このものをｎ−ヘキサンより再結晶し、（±）−９−ep
i−ノルアンブレノリド（下記構造式）を得た。融点93
〜94℃ 実施例２ 4,8,12−トリメチル−3,7,11−トリデカトリエン−１−
オール400mgのニトロプロパン1ml溶液を窒素雰囲気下に
おいて、−60〜70℃に冷却したクロルスルホン酸1.0gの
２−ニトロプロパン20ml溶液に滴下した。２時間撹拌
後、反応液を氷50gに注ぎ、エーテル抽出した。エーテ
ル層を重曹水で洗浄した後、硫酸マグネシウムで乾燥
し、溶媒を留去した。得られた油状物質をシリカゲルカ
ラムクロマトグラフィーにより分離し、アンブロックス
画分として320mgを得た。このものをガスクロマトグラ
フィーにより分析したところ下記構造式a:b＝4:96の混
合物であることが認められた。 This product was recrystallized from n-hexane to give (±) -9-ep
An i-norambrenolide (the following structural formula) was obtained. Melting point 93
~ 94 ° C Example 2 4,8,12-Trimethyl-3,7,11-tridecatriene-1-
A solution of 400 mg of nitropropane in 1 ml was added dropwise under nitrogen atmosphere to a solution of 1.0 g of chlorosulfonic acid in 20 ml of 2-nitropropane cooled at -60 to 70 ° C. After stirring for 2 hours, the reaction solution was poured into 50 g of ice and extracted with ether. The ether layer was washed with aqueous sodium hydrogen carbonate, dried over magnesium sulfate, and the solvent was evaporated. The obtained oily substance was separated by silica gel column chromatography to obtain 320 mg as an unblocked fraction. When this product was analyzed by gas chromatography, it was confirmed to be a mixture of the following structural formulas a: b = 4: 96.
実施例３ 5,9,13−トリメチル−4,8,12−テトラデカトリエン酸1.
3gのニトロプロパン5ml溶液を窒素雰囲気下において、
−60〜70℃に冷却したクロルスルホン酸2.6gの２−ニト
ロプロパン20ml溶液に滴下した。20分間撹拌後、反応液
を氷50gに注ぎ、エーテル抽出した。エーテル層を重曹
水で洗浄した後、硫酸マグネシウムで乾燥し、溶媒を留
去した。得られた油状物質をシリカゲルカラムクロマト
グラフィーにより分離した。ベンゼン−酢酸エチル（4:
1）溶出画分として得られた物質をｎ−ヘキサンより再
結晶することにより、（±）−アンブレノリド（下記構
造式）920mgを得た。融点132〜134℃ 実施例４ 5,9,13−トリメチル−4,8,12−テトラデカトリエノール
300mgを窒素雰囲気下において、−60℃にてクロルスル
ホン酸1.3gの２−ニトロプロパン20ml溶液に滴下した。
20分間撹拌後、反応液を氷50gに注ぎ、エーテル抽出し
た。エーテル層を重曹水で洗浄した後、硫酸マグネシウ
ムで乾燥し、溶媒を留去した。 Example 3 5,9,13-Trimethyl-4,8,12-tetradecatrienoic acid 1.
3 g of nitropropane 5 ml solution under nitrogen atmosphere,
It was added dropwise to a solution of 2.6 g of chlorosulfonic acid cooled to −60 to 70 ° C. in 20 ml of 2-nitropropane. After stirring for 20 minutes, the reaction solution was poured into 50 g of ice and extracted with ether. The ether layer was washed with aqueous sodium hydrogen carbonate, dried over magnesium sulfate, and the solvent was evaporated. The obtained oily substance was separated by silica gel column chromatography. Benzene-ethyl acetate (4:
1) The substance obtained as the elution fraction was recrystallized from n-hexane to obtain 920 mg of (±) -ambrenolide (the following structural formula). Melting point 132-134 ° C Example 4 5,9,13-Trimethyl-4,8,12-tetradecatrienol
300 mg was added dropwise to a solution of 1.3 g of chlorosulfonic acid in 20 ml of 2-nitropropane at −60 ° C. under a nitrogen atmosphere.
After stirring for 20 minutes, the reaction solution was poured into 50 g of ice and extracted with ether. The ether layer was washed with aqueous sodium hydrogen carbonate, dried over magnesium sulfate, and the solvent was evaporated.
得られた油状物質をシリカゲルカラムクロマトグラフィ
ーにより分離した。ベンゼン−酢酸エチル（4:1）溶出
画分としてアンブラオキシドの異性体混合物180mgを得
た。この物質をガスクロマトグラフィーにより分析し、
（±）−アンブラオキシド82％、９−epi体18％を含む
ことを確認した。（下記構造式） 実施例５ ７−（2,6,6−トリメチル−１−シクロヘキセニル）−
５−メチル−４−ヘプテン−１−オール300mgを窒素雰
囲気下において、−60℃にてクロルスルホン酸1.3gの２
−ニトロプロパン20ml溶液に滴下した。20分間撹拌後、
反応液を氷50gに注ぎ、エーテル抽出した。エーテル層
を重曹水で洗浄した後、硫酸マグネシウムで乾燥し、溶
媒を留去した。The obtained oily substance was separated by silica gel column chromatography. 180 mg of an isomer mixture of ambra oxide was obtained as a fraction eluted with benzene-ethyl acetate (4: 1). This material was analyzed by gas chromatography,
It was confirmed to contain (±) -umbra oxide 82% and 9-epi body 18%. (The following structural formula) Example 5 7- (2,6,6-Trimethyl-1-cyclohexenyl)-
300 mg of 5-methyl-4-hepten-1-ol was added to 1.3 g of chlorosulfonic acid at -60 ° C. under a nitrogen atmosphere.
-Drop to a 20 ml solution of nitropropane. After stirring for 20 minutes,
The reaction solution was poured into 50 g of ice and extracted with ether. The ether layer was washed with aqueous sodium hydrogen carbonate, dried over magnesium sulfate, and the solvent was evaporated.
得られた油状物質をシリカゲルカラムクロマトグラフィ
ーにより分離した。ベンゼン−酢酸エチル（4:1）溶出
画分としてアンブラオキシドの異性体混合物195mgを得
た。この物質をガスクロマトグラフィーにより分析し、
（±）−アンブラオキシド82％、９−epi体18％を含む
ことを確認した。The obtained oily substance was separated by silica gel column chromatography. As a benzene-ethyl acetate (4: 1) elution fraction, 195 mg of an isomer mixture of ambraoxide was obtained. This material was analyzed by gas chromatography,
It was confirmed to contain (±) -umbra oxide 82% and 9-epi body 18%.
実施例６ ７−（2,6,6−トリメチル−２−シクロヘキセニル）−
５−メチル−４−ヘプテン−１−オール370mgを窒素雰
囲気下、−70℃にてクロルスルホン酸800mgのジクロル
メタン20ml溶液に滴下した。30分間撹拌後、反応液を氷
50gに注ぎ、エーテル抽出した。エーテル層を重曹水で
洗浄した後、硫酸マグネシウムで乾燥し、溶媒を留去し
た。得られた油状物質をシリカゲルカラムクロマトグラ
フィーにより分画した。ベンゼン−酢酸エチル（4:1）
溶出画分としてアンブラオキシドの異性体混合物150mg
を得た。この物質をガスクロマトグラフィーにより分析
し、（±）−アンブラオキシド11％、９−epi体31％、1
0−epi体（下記構造式）58％を含むことを確認した。Example 6 7- (2,6,6-Trimethyl-2-cyclohexenyl)-
Under a nitrogen atmosphere, 370 mg of 5-methyl-4-hepten-1-ol was added dropwise to a solution of 800 mg of chlorosulfonic acid in 20 ml of dichloromethane at -70 ° C. After stirring for 30 minutes, cool the reaction mixture to ice.
It was poured into 50 g and extracted with ether. The ether layer was washed with aqueous sodium hydrogen carbonate, dried over magnesium sulfate, and the solvent was evaporated. The obtained oily substance was fractionated by silica gel column chromatography. Benzene-ethyl acetate (4: 1)
150 mg of isomer mixture of Umbra oxide as elution fraction
Got This substance was analyzed by gas chromatography to find that (±) -umbra oxide 11%, 9-epi form 31%, 1
It was confirmed to contain 58% of 0-epi body (the following structural formula).
実施例７ ７−（2,6,6−トリメチル−１−シクロヘキセニル）−
５−メチル−４−ヘプテン酸1.3gのニトロプロパン5ml
溶液を窒素雰囲気下において、−60〜70℃に冷却したク
ロルスルホン酸2.6gの２−ニトロプロパン20ml溶液に滴
下した。20分間撹拌後、反応液を氷50gに注ぎ、エーテ
ル抽出した。エーテル層を重曹水で洗浄した後、硫酸マ
グネシウムで乾燥し、溶媒を留去した。得られた油状物
質をシリカゲルカラムクロマトグラフィーにより分離し
た。ベンゼン−酢酸エチル（4:1）溶出画分として得ら
れた物質をｎ−ヘキサンより再結晶することにより、
（±）−アンブレノリド910mgを得た。 Example 7 7- (2,6,6-trimethyl-1-cyclohexenyl)-
5-Methyl-4-heptenoic acid 1.3 g nitropropane 5 ml
The solution was added dropwise under nitrogen atmosphere to a solution of 2.6 g of chlorosulfonic acid cooled in -60 to 70 ° C in 20 ml of 2-nitropropane. After stirring for 20 minutes, the reaction solution was poured into 50 g of ice and extracted with ether. The ether layer was washed with aqueous sodium hydrogen carbonate, dried over magnesium sulfate, and the solvent was evaporated. The obtained oily substance was separated by silica gel column chromatography. By recrystallizing the substance obtained as a benzene-ethyl acetate (4: 1) elution fraction from n-hexane,
(±) -Ambrenolide 910 mg was obtained.
実施例８ ６−（2,6,6−トリメチル−１−シクロヘキセニル）−
４−メチル−３−ヘキサン酸1.2gの２−ニトロプロパン
2ml溶液を窒素雰囲気下において、−70℃に冷却したク
ロルスルホン酸4.0gの２−ニトロプロパン18ml溶液に２
分間で滴下した。20分間撹拌後、反応液を氷50gに注
ぎ、エーテル抽出した。エーテル層を重曹水で洗浄した
後、硫酸マグネシウムで乾燥し、溶媒を留去した。得ら
れた油状物質をシリカゲルカラムクロマトグラフィーに
より分離し、（±）−ノルアンブレノリド0.84gを得
た。Example 8 6- (2,6,6-trimethyl-1-cyclohexenyl)-
4-Methyl-3-hexanoic acid 1.2 g of 2-nitropropane
2 ml of the solution was added to an 18 ml solution of 2-nitropropane containing 4.0 g of chlorosulfonic acid cooled at -70 ° C under a nitrogen atmosphere.
Dropped in minutes. After stirring for 20 minutes, the reaction solution was poured into 50 g of ice and extracted with ether. The ether layer was washed with aqueous sodium hydrogen carbonate, dried over magnesium sulfate, and the solvent was evaporated. The obtained oily substance was separated by silica gel column chromatography to obtain 0.84 g of (±) -norambrenolide.
実施例９ ６−（2,6,6−トリメチル−１−シクロヘキセニル）−
４−メチル−３−ヘキサン−１−オール500mgのニトロ
プロパン1ml溶液を窒素雰囲気下において、−65℃に冷
却したクロルスルホン酸1.0gの２−ニトロプロパン20ml
溶液に滴下した。30分間撹拌後、反応液を氷水50gに注
ぎ、エーテル抽出した。エーテル層を重曹水で洗浄した
後、硫酸マグネシウムで乾燥し、溶媒を留去した。得ら
れた油状物質をシリカゲルカラムクロマトグラフィーに
より分離し、アンブロックス画分として300mgを得た。
このものをガスクロマトグラフィーにより分析したとこ
ろ（±）−アンブロックス23％、９−epi体77％を含む
ことが確認された。Example 9 6- (2,6,6-trimethyl-1-cyclohexenyl)-
A solution of 500 mg of 4-methyl-3-hexan-1-ol in 1 ml of nitropropane was cooled to -65 ° C under a nitrogen atmosphere, and 20 ml of 2-nitropropane containing 1.0 g of chlorosulfonic acid was cooled.
Dropped into the solution. After stirring for 30 minutes, the reaction solution was poured into 50 g of ice water and extracted with ether. The ether layer was washed with aqueous sodium hydrogen carbonate, dried over magnesium sulfate, and the solvent was evaporated. The obtained oily substance was separated by silica gel column chromatography to obtain 300 mg as an unblocked fraction.
When this product was analyzed by gas chromatography, it was confirmed that it contained (±) -unblocks 23% and 9-epi isomer 77%.
本発明は、化合物（II）もしくは化合物（III）を反応
原料に用いて経済的かつ安全に化合物（Ｉ）を製造する
方法を提供する。The present invention provides a method for economically and safely producing compound (I) using compound (II) or compound (III) as a reaction raw material.
Claims (1)
＝Ｏを表し、ＲはＡがCH2を表すときは水素原子もしく
は炭素数１〜４のアシル基を表し、ＡがＣ＝Ｏを表すと
きは水素原子もしくは炭素数１〜４のアルキル基を表
す。） で示される化合物、又は下記一般式 （式中、ｎ、ＡおよびＲは式（II）におけるのと同じ意
味を表す。） で示される化合物をクロルスルホン酸と反応させた後、
水で処理することを特徴とする下記一般式 （式中、ｎおよびＡは式（II）におけるのと同じ意味を
表す。） で示される環状テルペン化合物の製造方法。1. The following general formula (In the formula, n represents 1 or 2, A is CH 2 or C
═O, R represents a hydrogen atom or an acyl group having 1 to 4 carbon atoms when A represents CH 2, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms when A represents C═O. Represent ) Or a compound represented by the following general formula (In the formula, n, A and R have the same meanings as in formula (II).) After reacting the compound represented by: with chlorosulfonic acid,
The following general formula characterized by treatment with water (In the formula, n and A have the same meanings as in formula (II).) A method for producing a cyclic terpene compound represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8059589A JPH0694463B2 (en) | 1989-03-30 | 1989-03-30 | Method for producing cyclic terpene compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8059589A JPH0694463B2 (en) | 1989-03-30 | 1989-03-30 | Method for producing cyclic terpene compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02258773A JPH02258773A (en) | 1990-10-19 |
| JPH0694463B2 true JPH0694463B2 (en) | 1994-11-24 |
Family
ID=13722689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8059589A Expired - Fee Related JPH0694463B2 (en) | 1989-03-30 | 1989-03-30 | Method for producing cyclic terpene compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0694463B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2525085B2 (en) * | 1991-02-19 | 1996-08-14 | 株式会社クラレ | Iron manufacturing method |
| US5329053A (en) * | 1992-09-03 | 1994-07-12 | Givaudan-Roure Corporation | Process for the manufacture of known odorants |
| DE4301555C1 (en) * | 1993-01-21 | 1994-07-07 | Henkel Kgaa | Process for the production of norambreinolide |
-
1989
- 1989-03-30 JP JP8059589A patent/JPH0694463B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02258773A (en) | 1990-10-19 |
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