JPS59225176A - Production of linalool oxide - Google Patents
Production of linalool oxideInfo
- Publication number
- JPS59225176A JPS59225176A JP10017683A JP10017683A JPS59225176A JP S59225176 A JPS59225176 A JP S59225176A JP 10017683 A JP10017683 A JP 10017683A JP 10017683 A JP10017683 A JP 10017683A JP S59225176 A JPS59225176 A JP S59225176A
- Authority
- JP
- Japan
- Prior art keywords
- type
- linalool
- reaction
- pyran
- furan
- 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
Abstract
Description
【発明の詳細な説明】
本発明はりナロールオキサイドの製造法、更に詳細には
下記の一般式（Ｉ）で示されるシス盟友ヒトランス型２
−メチル−２−ビニル−５−ハイドロキシ−イソプロピ
ルテトラハイドロフラン（フラン型）
フラン型（Ｉ）
及び下記の一般式（ＩＴ）で示されるシス型及びトラン
ス型２，６，６−）ジメチル−２−ビニル−５−ハイド
ロキシ−テトラハイドロピラン（ピラン型）
の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing alinarol oxide, more specifically, to the cis-alternate hytrans-type 2 represented by the following general formula (I).
-Methyl-2-vinyl-5-hydroxy-isopropyltetrahydrofuran (furan type) Furan type (I) and cis-type and trans-type 2,6,6-) dimethyl-2 represented by the following general formula (IT) - A method for producing vinyl-5-hydroxy-tetrahydropyran (pyran type).
一般式（Ｉ）及び（ＩＩ）で示される化合物は通称リナ
ロールオキサイドとして公知であり、多くの香料植物油
に含有され、フラン型（Ｉｌは例えばセラニウム、ラベ
ンダー、ラバンジン、リナロ工、オスマンタス等の合成
精油の有用な調合素材とし使用され、またピラン型（Ｉ
Ｉ）は下記式化合物のような興味ある香料化合物の合成
中間体どして１吏用できる。The compounds represented by the general formulas (I) and (II) are commonly known as linalool oxide, and are contained in many fragrant vegetable oils. It is used as a useful compounding material for pyran-type (I)
I) can be used as an intermediate for the synthesis of perfume compounds of interest such as compounds of the formula:
（Ｄ、Ｒ，Ａ＋ＩａｌｌＩｓ Ｆｆａｖｏｕｒｓ、１
８５〜１８８．１９７３）（岡崎等；日本化学会誌、３
５５〜３５９．１９７３１従来、リナロールからのりナ
ロールオキサイド（一般式（Ｉ）及び（ＩＩ）の合成法
に関してはりナロールζこモノ過フタル酸を作用させて
エポキシリナロールとし、次に加熱または酸処理してリ
ナロールオキサイド〔フラン型（Ｉ）とピラン型（ｎ）
（７）生成比率９０： １０）を得る方法（Ｄ、Ｆ
ａｌｉｚｅｔａｌ ； ［（ｅｌｖ、、４８．＋５１３
（＋９８３））またメチレンクロライド溶媒中のりナロ
ールに過酢酸を作用させてリナロールオキサイドを得る
方法〔フラノ型（Ｉ）とピラン型（ＩＩＩの生成比率８
２： １８］等が報告［Ｅ、Ｋｌｅｉｎ ｅｔ ａト
Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ、Ｎｏ １７
、１１０９． （１９６３） ）されているに過ぎない
。(D, R, A+IallIs Ffavors, 1
85-188.1973) (Okazaki et al.; Journal of the Chemical Society of Japan, 3
55-359.19731 Conventionally, linalool is made into epoxy linalool by reacting linalool with monoperphthalic acid (regarding the synthesis method of general formulas (I) and (II)), and then heated or treated with acid. linalool oxide [furan type (I) and pyran type (n)
(7) Method for obtaining a production ratio of 90: 10 (D, F
alizetal; [(elv,,48.+513
(+983)) Also, a method for obtaining linalool oxide by reacting peracetic acid with linalol in a methylene chloride solvent [production ratio of furano type (I) and pyran type (III): 8
2: 18] and others reported [E, Klein et al. Tetrahedron Letters, No. 17
, 1109. (1963)).
本発明は、１段階の簡単な操作によりリナロールオキサ
イドを高収率にて製造する方法を提供することを目的と
する。また、本発明によれば、従来法に比較しピラン型
＋ＩＩ）の異性体に富むリナロールオキサイドの製造法
が提供される。An object of the present invention is to provide a method for producing linalool oxide in high yield through a simple one-step operation. Further, according to the present invention, there is provided a method for producing linalool oxide which is richer in pyran type +II) isomer than conventional methods.
本発明によれば、下記の一般式で示されるリナロール
ロキシル化と閉環を行って下記の一般式で示されろフラ
ン型のりナロールオキサイド
オキサイド
の製造法が提供される。According to the present invention, there is provided a method for producing linalool oxide represented by the following general formula by performing linalool oxylation and ring closure represented by the following general formula.
以下、本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明考等はりナロールオキサイドの経済的且工業的製
造法に関して鋭意検討した結果、下記反応式に示した如
く、リナロール（ＩＶ）に酸性条件下ヒドロキシル化剤
を作用させる事により、ヒドロキシル化、次の閉環（脱
水）の両反応が連続して速かに進行し、反応中間体（Ｉ
ＩＩＩを反応寝装から単離することなしに一工程の操作
で８０％以上の高収率でリナロールオキサイド〔フラン
型（Ｉｌとピラン型（１）の生成比率６０〜７０：４０
〜３０〕が生成することを見出だした。As a result of intensive studies on the economical and industrial production method of linalool oxide, the inventors of the present invention found that, as shown in the reaction formula below, linalool (IV) is hydroxylated by reacting with a hydroxylating agent under acidic conditions. Both the subsequent ring-closing (dehydration) reactions proceed continuously and rapidly, producing the reaction intermediate (I
Linalool oxide [furan type (Il and pyran type (1) production ratio: 60-70:40) in a high yield of 80% or more in one step without isolating III from the reaction bed.
~30] was found to be generated.
ピラン型（ＩＩ）
本発明の実施に際して使用し得る適当なヒドロキシル化
剤としては硫酸などの鉱酸水溶液存在下の有機過酸又は
有機過酸と過酸水素との混合物を挙げることができる。Pyran Type (II) Suitable hydroxylating agents that may be used in the practice of this invention include organic peracids or mixtures of organic peracids and hydrogen peroxide in the presence of aqueous mineral acids such as sulfuric acid.
有機過酸としては、たとえば過蟻酸、過酢酸、過プロピ
４ン酸、過酢酸、過安息香酸、モノ過フタル酸等を挙げ
ることができる。上述のヒドロキシル化剤のうちで特に
工業的に有利に使用できるものは過！ｌ！ｉｌ酸及び硫
酸存在下の過酢酸である。Examples of the organic peracid include performic acid, peracetic acid, perpropyl tetranic acid, peracetic acid, perbenzoic acid, and monoperphthalic acid. Among the above-mentioned hydroxylating agents, those that can be used industrially with particular advantage are hydroxylating agents. l! peracetic acid in the presence of il acid and sulfuric acid.
リナロールに対してのヒドロキシル化剤の使用量（モル
当量）は通常０５〜５０倍モルの範囲、好ましくは１〜
１５倍モルの範囲で使用できるが、必ずしも臨界的なも
のではない。反応温度は０〜１００℃の範囲、好ましく
は２０〜８０℃の範囲て実施することができる。本反応
は本質的に発熱反応であり、反応温度の降下現象は反応
が終了に近づいていることを示す。反応完結の確認はガ
スクロ分析（Ｐ、 Ｅ、 Ｇ−２０Ｍ、 ＴＰＰＯ２３
ｍｍ Ｘ ２ ｍ 、カラム温度１３０℃）によって分
析することができる。The amount (mole equivalent) of the hydroxylating agent used relative to linalool is usually in the range of 05 to 50 times, preferably 1 to 50 times the molar amount.
It can be used in a 15-fold molar range, but this is not necessarily critical. The reaction temperature can be carried out in the range of 0 to 100°C, preferably in the range of 20 to 80°C. This reaction is essentially exothermic, and the phenomenon of a drop in reaction temperature indicates that the reaction is nearing completion. Confirmation of reaction completion was performed by gas chromatography (P, E, G-20M, TPPO23
mm x 2 m, column temperature 130°C).
以下、本発明を実施例につき説明する。なお、％は重量
基準を示す。Hereinafter, the present invention will be explained with reference to examples. Note that % indicates a weight basis.
実施例−１
かきまぜ機、還流冷却管、温度計及び滴下ロートを装備
した内容２１の四ツロフラスコにリナロール１５４ ｇ
（］、Ｏｍｏｌ）及び４０％蟻酸１１５ｇ（１，０モ
ル）を仕込んだ。油浴にて反応液を６０〜６５℃に加渇
し、激しくかきまぜながら３０％過酸化水素１３６ｇ（
１，２モル）滴下ロートより約１時開票して滴下した。Example-1 154 g of linalool was placed in a four-way flask with content 21 equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel.
(], Omol) and 115 g (1.0 mol) of 40% formic acid were charged. The reaction solution was heated to 60-65°C in an oil bath, and while stirring vigorously, 136 g of 30% hydrogen peroxide (
1.2 mol) was added dropwise from the dropping funnel at about 1 o'clock.
その際、反応温度は６５〜７５℃に保持した。更に反応
完結の為、同温度で約２時間かきまぜた。反応終了後、
′飽和食塩水４００ｍｊ及びベンゼン３００ ｍ ｌを
加え、約１０分間かきまぜた後分液ロートに移し有機層
と水層を分離し、有機層は１０％炭酸ソーダ水溶液で中
和し水洗、乾燥後ベンゼンを留去し、残渣１３９ｇを得
た。その残渣をガスクロマトグラフ分析した結果、次の
組成を示した。At that time, the reaction temperature was maintained at 65 to 75°C. Further, in order to complete the reaction, the mixture was stirred at the same temperature for about 2 hours. After the reaction is complete,
'Add 400 mj of saturated brine and 300 ml of benzene, stir for about 10 minutes, then transfer to a separatory funnel to separate the organic and aqueous layers.The organic layer is neutralized with a 10% aqueous sodium carbonate solution, washed with water, dried, and then washed with benzene. was distilled off to obtain 139 g of a residue. Gas chromatography analysis of the residue showed the following composition.
シス−及びトランス−フラン型（Ｉｌ リナロールオ
キサイド ５８７％副生成物 ７０
％
シス−及びトランス−ピラン型（ＩＩ） リナロール
オキサイド ３４３％前記残渣１３９ｇを減圧蒸留した
結果、沸点４６〜５０℃／ １ ＋ｎｍ Ｈｇのフラン
型（Ｉ） リナロールオキサイドに相当する留分８４
ｇ及び沸点７０〜７２℃／ １ ＋ｍｎ ｌ（ｇのピラ
ン型（ＩＩ） リナロールオキサイドに相当する留分
４１ｇを得た。収量は１２５ｇ（実収率８１２％）であ
った。Cis- and trans-furan types (Il Linalool oxide 587% by-products 70
% cis- and trans-pyran type (II) linalool oxide 343% As a result of vacuum distillation of 139 g of the above residue, a fraction 84 corresponding to furan type (I) linalool oxide with a boiling point of 46-50°C/1 + nm Hg
41 g of a fraction corresponding to pyran type (II) linalool oxide with a boiling point of 70 to 72° C./1 + mn l (g) was obtained. The yield was 125 g (actual yield 812%).
物理恒数を下記に示す。The physical constants are shown below.
フラン型（Ｉｌ ： ｄ：： ０．９４＋８、ｎ’、
” １．４５０５ビラン型（ｒｘ）： ｄ：：
０．９９２８、ｎ’、’ １．４７６５実施例−２
実施例−１と同じ反応装置に４０％過酢酸２３４ｇ（１
２モル）及び５％硫酸２３４ｇを仕込んだ。Furan type (Il: d:: 0.94+8, n',
” 1.4505 Biran type (rx): d::
0.9928, n', ' 1.4765 Example-2 234 g of 40% peracetic acid (1
2 mol) and 234 g of 5% sulfuric acid were charged.
次に激しくかきまぜながら滴下ロートより、リナロール
１５４ｇ（１，０モル）を約１時開票して滴下した。そ
の際反応温度を２５〜３０℃に保持した。Next, while stirring vigorously, 154 g (1.0 mol) of linalool was added dropwise from the dropping funnel at about 1 hour. At that time, the reaction temperature was maintained at 25-30°C.
更に反応を完結させる為約２時間、同温度でかきまぜた
。その反応液を水冷の３０％−苛性ソーダ水溶液５００
ｇに注いで中和した。次にベンセン３００ｍｌを加え抽
出し、有機層を水洗、乾燥後ベンゼンを留去し、残渣１
３５ｇを得ｔ：、その残渣をガスクロマトグラフ分析し
た結果、次の組成を示した。The mixture was further stirred at the same temperature for about 2 hours to complete the reaction. The reaction solution was cooled with 30% caustic soda aqueous solution
It was neutralized by pouring it into g. Next, 300 ml of benzene was added and extracted, the organic layer was washed with water, and after drying, the benzene was distilled off, leaving a residue of 1.
35 g was obtained, and gas chromatographic analysis of the residue showed the following composition.
シス−及びトランス−フラン型（Ｉ） リナロールオ
キサイド ６６３％副生成物 １５
％
シス−及びトランス−ピラン型ｆｌｌ） リナロール
オキサイド ３２２％前記残渣１３５ｇを減圧蒸留した
結果、沸点４６〜ｂ
オキサイドに相当する留分８２ｇ及び沸点７０〜７２℃
７１ ｍｍ ［（ｇのピラン型（■）すＱナロールオキ
サイドに相当する留分４１５ｇを得た。収量は１２３５
ｇ（実収率８０２％）であった。Cis- and trans-furan type (I) linalool oxide 663% by-products 15
% cis- and trans-pyran type) Linalool oxide 322% As a result of vacuum distillation of 135 g of the above residue, 82 g of fraction corresponding to boiling point 46-b oxide and boiling point 70-72°C
415 g of a fraction corresponding to 71 mm [g of pyran-type (■) Q naol oxide was obtained. The yield was 1235
g (actual yield 802%).
物理恒数を下記に示す。The physical constants are shown below.
フラン型（Ｉ）＝ｄ：二 ０．９４２０、ｎ ：’
１．４５０９ピラン型＜ｍ）： ｄ：： ０．９９
３０、ｎ’：５１．４７６８７３１Furan type (I) = d: 2 0.9420, n:'
1.4509 pyran type <m): d:: 0.99
30, n': 51.4768731
Claims (2)
ル化と閉環を行って下記の一般式で示されるフラン型の
りナロールオキサイドルオキサイド ドの製造法。(1) A method for producing furan-type glue nalol oxide represented by the following general formula by carrying out linalool droxylation and ring closure.
又は有ｔｌＩ過酸と過酸化水素との混合物であることを
特徴とする特許請求の範囲第１項に記載の製造法。(2) The method according to claim 1, wherein the hydroxylating agent is a mixture of an organic peracid or a tlI peracid and hydrogen peroxide in the presence of a mineral acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10017683A JPS59225176A (en) | 1983-06-07 | 1983-06-07 | Production of linalool oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10017683A JPS59225176A (en) | 1983-06-07 | 1983-06-07 | Production of linalool oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59225176A true JPS59225176A (en) | 1984-12-18 |
| JPH0370704B2 JPH0370704B2 (en) | 1991-11-08 |
Family
ID=14267003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10017683A Granted JPS59225176A (en) | 1983-06-07 | 1983-06-07 | Production of linalool oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59225176A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6703218B2 (en) | 2000-11-07 | 2004-03-09 | Haarman & Reimer Gmbh | Process for the preparation of linalool oxide or of linalool oxide-containing mixtures |
| CN105801529A (en) * | 2016-05-22 | 2016-07-27 | 上海应用技术学院 | Preparation method for carbonic acid linalool oxide (pyran type and furan type) ester ethyl ester |
-
1983
- 1983-06-07 JP JP10017683A patent/JPS59225176A/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| LIEBIGS ANNALEN DER CHEMIE=1964 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6703218B2 (en) | 2000-11-07 | 2004-03-09 | Haarman & Reimer Gmbh | Process for the preparation of linalool oxide or of linalool oxide-containing mixtures |
| CN105801529A (en) * | 2016-05-22 | 2016-07-27 | 上海应用技术学院 | Preparation method for carbonic acid linalool oxide (pyran type and furan type) ester ethyl ester |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0370704B2 (en) | 1991-11-08 |
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