JPS5918381B2 - Method for producing isocamphane compound - Google Patents
Method for producing isocamphane compoundInfo
- Publication number
- JPS5918381B2 JPS5918381B2 JP9403677A JP9403677A JPS5918381B2 JP S5918381 B2 JPS5918381 B2 JP S5918381B2 JP 9403677 A JP9403677 A JP 9403677A JP 9403677 A JP9403677 A JP 9403677A JP S5918381 B2 JPS5918381 B2 JP S5918381B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- producing
- isocamphane
- exo
- glacial acetic
- 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
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- -1 isocamphane compound Chemical class 0.000 title 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 claims 2
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 claims 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims 1
- 229930006739 camphene Natural products 0.000 claims 1
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003205 fragrance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- CFXJOMGPUADAJE-XHNCKOQMSA-N (1s,4s,5r)-2,2-dimethyl-3-methylidenebicyclo[2.2.1]heptan-5-ol Chemical compound C1[C@@H](O)[C@@H]2C(=C)C(C)(C)[C@H]1C2 CFXJOMGPUADAJE-XHNCKOQMSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CFXJOMGPUADAJE-UHFFFAOYSA-N Nojigiku-Alkohol Natural products C1C(O)C2C(=C)C(C)(C)C1C2 CFXJOMGPUADAJE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
５ 本発明は次の一般式（Ｉ）
Ｉｏ（Ｉ）
ＡｃＯＣＨ３
１５（式中、Ａｃはアセチル基を示す）
で表わされる６−エキソ−アセトキシ−エキソ〜イソガ
ンファンの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION 5 The present invention provides 6-exo-acetoxy-exo-isoganphane represented by the following general formula (I) Io(I) AcOCH3 15 (wherein Ac represents an acetyl group). Regarding the manufacturing method.
更に詳細には、本発明は次の反応式によつて示される。More specifically, the present invention is illustrated by the following reaction formula.
３θ
すなわち、本発明は、ガンフェン（）に氷酢酸および濃
硫酸を作用せしめて、６−エキソーアセトキシーエキソ
ーイソカンフアン（１）を製造する方法である。3θ That is, the present invention is a method for producing 6-exoacetoxyexoisocamphane (1) by reacting ganfen () with glacial acetic acid and concentrated sulfuric acid.
而して、本発明方法で得られる６−エキソーアセトキシ
ーエキソーイソカンフアン（１）はノジギクアセテート
に類似した芳香を有し、菊様香料の原料として重要な化
合物である。Thus, 6-exoacetoxyexoisocamphane (1) obtained by the method of the present invention has a fragrance similar to Nojikiku acetate, and is an important compound as a raw material for chrysanthemum-like fragrances.
６−エキソーアセトキシーエキソーイソカンフ＊氷フア
ン（１）は、従来、すでに、ガンフェンとフエノールを
三弗化ホウ素の存在下縮合し、その縮合生成物の１つで
ある６−エキソ−０−ヒドロキシフエニルーエキソーイ
ソカンフアンから次に示す数工程を経て（１）式の化合
物を製造する方法が報告されている〔Ｗ．Ｆ．Ｅｒｍａ
ｎ；Ｊ．Ａｍｅｒ．Ｃｈｅｍ．ＳＯｃ．、生ρ、２８８
７（１９６４）〕が、その収率は６％に過ぎない。6-Exo-acetoxy-Exo-isocamphu *Hyohuan (1) has conventionally been produced by condensing ganphene and phenol in the presence of boron trifluoride, and producing 6-exo-0, one of the condensation products. A method for producing the compound of formula (1) from -hydroxyphenyl-exoisocamphane through the following several steps has been reported [W. F. Erma
n;J. Amer. Chem. SOc. , Raw ρ, 288
7 (1964)], but the yield is only 6%.
本発明者はこの工業的製造法について研究を行つていた
ところ、ガンフェン（）を氷酢酸と濃硫酸で処理する、
所謂ベルトラムーバルバウム（Ｂｅｒｔｒａｍ−Ｗａｌ
ｂａｕｍ）水和反応に付せば、一挙に約２０％の収率で
（１）式の化合物が得られ ！ることを見出した。While researching this industrial production method, the present inventor discovered that Ganfen (2017) was treated with glacial acetic acid and concentrated sulfuric acid.
The so-called Bertram-Wal
baum), the compound of formula (1) can be obtained at once with a yield of about 20%! I discovered that.
この反応は、ガンフェン１モルに対して氷酢酸８モル、
硫酸０．５モルを使用して、５０〜５５℃の温度で約６
時間行うのがよい結果を与える。In this reaction, 8 moles of glacial acetic acid per mole of ganfen,
using 0.5 mol of sulfuric acid at a temperature of 50-55°C.
Doing it for an hour gives good results.
本発明の方法で得られる６−エキソーアセトキシーエキ
ソーイソカンフアン（１）は、これを加水分解すること
により、容易に脱アセチル化し、香料成分として有用な
６−エキソーヒドロキシエキソーイソカンフアンに導く
ことができる。この化合物はノジギクアルコールに類似
した菊様の芳香を有する化合物で、その製法としては、
前述のＷ．Ｆ．Ｅｒｍａｎの方法と同様にして縮合を行
い、複雑な反応工程を経て１５％の収率で得る方法が知
られている〔Ｅ．ＤｅｍＯｌｅ：Ｈｅｌｖ．Ｃｈｉｍ．
Ａｃｔａ．５２（７）、２０６６（１９６９）〕。しか
し、（１）の化合物を常法、例えばアルコール性苛性ソ
ーダで加水分離すれば、ほ〜定量的収率で６−エキソー
ヒドロキシーエキソーイソカンフアンが得られる。次に
実施例及び参考例を挙げて説明する。6-Exoacetoxyexoisocamphane (1) obtained by the method of the present invention can be easily deacetylated by hydrolyzing it, and is useful as a fragrance ingredient. Can lead to Kung Huan. This compound has a chrysanthemum-like aroma similar to Nojigiku alcohol, and its manufacturing method is as follows:
The aforementioned W. F. A method is known in which condensation is carried out in a manner similar to the method of E. E., and a yield of 15% is obtained through complicated reaction steps [E. DemOle: Helv. Chim.
Acta. 52(7), 2066 (1969)]. However, if the compound (1) is hydrolyzed in a conventional manner, for example with alcoholic caustic soda, 6-exohydroxy-exoisocamphane can be obtained in a fairly quantitative yield. Next, examples and reference examples will be given and explained.
実施例
ガンフェン１３６７（１モル）に氷酢酸４８０ｙ（８モ
ル）を加え、これに濃硫酸４９ｔ（０．５モル）を添加
し、湯浴土５０〜５５℃で６時間攪拌した。Example 480 y (8 mol) of glacial acetic acid was added to Ganfen 1367 (1 mol), 49 t (0.5 mol) of concentrated sulfuric acid was added thereto, and the mixture was stirred at 50-55°C for 6 hours.
反応液に水、ヘキサンを加え、ヘキサン層を分別し、ヘ
キサン溶液を炭酸ナトリウム水溶液で中和、水洗し、無
水硫酸ナトリウムで乾燥した。次いでヘキサンを留去し
、水和生成物１８５７を得た。これをマクマホン式精留
塔で精留し、８９℃／４ｍ７７！Ｈｇの留分１５７を得
た。このものはガスクロマトグラフイ一分析で単一成分
であり、次の分析結果から６−エキソーアセトキシーエ
キソーイソカンフアンであることを確認した。１ノ′
元素分析値：．Ｃｌ２Ｈ２ＯＯ２として
参考例
６−エキソーアセトキシーエキソーイソカンフアン２０
７に１Ｎ一苛性ソーダ・エタノール溶液２００ｍ１を加
え、湯浴上８０℃にて２時間加熱した。Water and hexane were added to the reaction solution, the hexane layer was separated, the hexane solution was neutralized with an aqueous sodium carbonate solution, washed with water, and dried over anhydrous sodium sulfate. Hexane was then distilled off to obtain hydrated product 1857. This was rectified using a McMahon type rectification column to achieve a temperature of 89℃/4m77! Hg fraction 157 was obtained. Gas chromatography analysis revealed that this product was a single component, and the following analysis results confirmed that it was 6-exoacetoxyexoisocamphane. 1 no' Elemental analysis value:. Reference example 6-exoacetoxyexoisocamphane 20 as Cl2H2OO2
200 ml of 1N caustic soda/ethanol solution was added to 7 and heated at 80°C on a hot water bath for 2 hours.
Claims (1)
とを特徴とする式、▲数式、化学式、表等があります▼
（ I ）（式中、Ａｃはアセチル基を示す） で表わされる６−エキソ−アセトキシ−エキソ−イソカ
ンファンの製造方法。[Claims] 1. There are formulas, ▲mathematical formulas, chemical formulas, tables, etc., characterized by the action of camphene with glacial acetic acid and concentrated sulfuric acid▼
(I) A method for producing 6-exo-acetoxy-exo-isocamphane represented by (in the formula, Ac represents an acetyl group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9403677A JPS5918381B2 (en) | 1977-08-05 | 1977-08-05 | Method for producing isocamphane compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9403677A JPS5918381B2 (en) | 1977-08-05 | 1977-08-05 | Method for producing isocamphane compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5430144A JPS5430144A (en) | 1979-03-06 |
| JPS5918381B2 true JPS5918381B2 (en) | 1984-04-26 |
Family
ID=14099331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9403677A Expired JPS5918381B2 (en) | 1977-08-05 | 1977-08-05 | Method for producing isocamphane compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5918381B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6165676U (en) * | 1984-10-03 | 1986-05-06 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57204022U (en) * | 1981-06-16 | 1982-12-25 | ||
| JPS6417319U (en) * | 1987-07-22 | 1989-01-27 |
-
1977
- 1977-08-05 JP JP9403677A patent/JPS5918381B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6165676U (en) * | 1984-10-03 | 1986-05-06 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5430144A (en) | 1979-03-06 |
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