JPH07310089A - Perfume comprising 1-oxaspiro(2. 5)octane-2-carboxylic acid ester - Google Patents
Perfume comprising 1-oxaspiro(2. 5)octane-2-carboxylic acid esterInfo
- Publication number
- JPH07310089A JPH07310089A JP10526594A JP10526594A JPH07310089A JP H07310089 A JPH07310089 A JP H07310089A JP 10526594 A JP10526594 A JP 10526594A JP 10526594 A JP10526594 A JP 10526594A JP H07310089 A JPH07310089 A JP H07310089A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- oxaspiro
- octane
- perfume
- carboxylic 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は香料組成物に関する。さ
らに詳しくは、本発明は一般式（１）This invention relates to fragrance compositions. More specifically, the present invention relates to general formula (1)
【化２】 （式中、Ｒ1は水素あるいは炭素数１〜４のアルキル基
を示し、Ｒ2は炭素数１〜４のアルキル基を示す）で表
される１−オキサスピロ（２.５）オクタン−２−カル
ボン酸エステルからなる香料およびこれを含有する香料
組成物に関する。本発明の香料および香料組成物は食
品、化粧品、室内芳香剤などの香料素材として有用であ
る。[Chemical 2] (In the formula, R 1 represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 2 represents an alkyl group having 1 to 4 carbon atoms.) 1-oxaspiro (2.5) octane-2- The present invention relates to a fragrance comprising a carboxylic acid ester and a fragrance composition containing the fragrance. The perfume and the perfume composition of the present invention are useful as a perfume material for foods, cosmetics, indoor air fresheners and the like.
【０００２】[0002]
【従来の技術】従来、本発明化合物（１）に近縁のエポ
キシ構造を有する香料として、例えば、下記式（２）を
有するα−アルキル置換−β−メチル−β−フェニルグ
リシド酸エステル（特開平２−７２１６８）、下記式
（３）を有するグリシド酸エステル（特開昭５７−３５
５０８）などが知られている。Conventionally, as a fragrance having an epoxy structure closely related to the compound (1) of the present invention, for example, an α-alkyl-substituted-β-methyl-β-phenylglycidate ester having the following formula (2) ( JP-A-2-72168), glycidic acid ester having the following formula (3) (JP-A-57-35)
508) and the like are known.
【０００３】[0003]
【化３】 [Chemical 3]
【０００４】上記式中、Ｒ′1およびＲ′2はメチル基ま
たはエチル基を表し、Ｒ″1は炭素数１〜１１個のアル
キリデン基または炭素数２〜１１個のアルケニル基であ
り、点線はＲ″1がアルキリデン基である場合には二重
結合になることを示し、Ｒ″2は水素または炭素数１〜
７個のアルキル基を表し、そしてＲ″3は炭素数１〜５
個のアルキル基を表す。上記式（２）の化合物は果実様
或いは花香様を想起させる特有の甘さと優れた保留性を
有し、また、上記式（３）の化合物は各種の香水のベー
スや化粧品、セッケン、日用品などの賦香剤として用い
られるほか、フレーバー成分、合成精油成分、防臭剤成
分、消臭剤成分および香料希釈剤などに広く用いられる
とされている。[0004] In the above formulas, R '1 and R' 2 represents a methyl group or an ethyl group, R "1 is the number 1 to 11 or alkylidene group or a carbon number 2 to 11 alkenyl group having a carbon dotted Indicates that R ″ 1 becomes a double bond when R ″ 1 is an alkylidene group, and R ″ 2 is hydrogen or 1 to 1 carbon atoms.
Represents 7 alkyl groups, and R ″ 3 has 1 to 5 carbon atoms
Represents an alkyl group. The compound of formula (2) has a peculiar sweetness that reminds of a fruity or floral scent and has an excellent retaining property, and the compound of formula (3) is a base of various perfumes, cosmetics, soaps, daily necessities, etc. In addition to being used as a flavoring agent, it is widely used as a flavor component, a synthetic essential oil component, a deodorant component, a deodorant component, a perfume diluent, and the like.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、フルーツ
様、トロピカル様の甘い香りを有するよりすぐれた香料
および香料組成物を提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide superior perfumes and perfume compositions having a fruity, tropical-like sweet scent.
【０００６】[0006]
【課題を解決するための手段】本発明は、前記式（１）
を有する１−オキサスピロ（２.５）オクタン−２−カ
ルボン酸エステルからなる香料およびこれを含有する香
料組成物よりなる。前記式（１）のＲ1およびＲ2の定義
において、アルキル基は直鎖状または分枝鎖状のアルキ
ル基を意味し、その例として、メチル、エチル、ｎ−プ
ロピル、iso−プロピル、ｎ−ブチルなどがあげられ
る。前記式（１）の化合物およびその製法は文献、例え
ば、Organic Reactions, vol.5, p.427 (1949）に記載
されているが、この化合物が香料として使用し得ること
は記載されていない。前記式（１）を有する化合物は、
トロピカルフルーツ様の甘い香りを有し、香料組成物に
添加することによってその香料組成物の甘さを強調し、
全体をエキゾチックな香りとする性質を有している。本
発明の香料組成物における前記式（１）の化合物の含有
量は、約０.５〜１０重量％であり、約３〜６重量％と
するのが望ましい。本発明の香料組成物は常法にしたが
って各香料を溶媒に溶かし、混合することによって製造
される。The present invention is based on the above formula (1).
And a fragrance composition containing 1-oxaspiro (2.5) octane-2-carboxylic acid ester. In the definition of R 1 and R 2 in the above formula (1), the alkyl group means a linear or branched alkyl group, and examples thereof include methyl, ethyl, n-propyl, iso-propyl, n. -Butyl and the like. The compound of the above formula (1) and its production method are described in the literature, for example, Organic Reactions, vol.5, p.427 (1949), but it is not described that this compound can be used as a fragrance. The compound having the above formula (1) is
It has a tropical fruit-like sweet scent and emphasizes the sweetness of the fragrance composition by adding it to the fragrance composition,
It has the property of giving the whole an exotic scent. The content of the compound of formula (1) in the perfume composition of the present invention is about 0.5 to 10% by weight, preferably about 3 to 6% by weight. The fragrance composition of the present invention is produced by dissolving each fragrance in a solvent and mixing them according to a conventional method.
【０００７】また、前記式（１）の化合物は、例えば上
記の文献に記載された方法に従って、式（４）The compound of the formula (1) can be obtained by the method of the formula (4) according to the method described in the above-mentioned document.
【化４】 （式中、Ｒ1およびＲ2は前述したものと同一意義を有す
る）を有する化合物を塩基の存在下に、シクロヘキサン
と混合することによって容易に製造される。[Chemical 4] It is easily prepared by mixing a compound having the formula (wherein R 1 and R 2 have the same meaning as described above) with cyclohexane in the presence of a base.
【０００８】[0008]
【実施例】次に参考例および実施例を示して本発明をさ
らに具体的に説明する。 参考例１ メチル ２−クロロプロピオナート９８ｇとシクロヘキ
サノン４９ｇをエーテル２００mlに溶解し、０℃に冷却
した。窒素気流下、ナトリウムメトキシド（９５％パウ
ダー）４５.５ｇを徐々に加えた。反応終了後、０.５規
定塩酸水溶液２００mlで洗浄した。次いで、飽和重曹水
１００mlと飽和食塩水２００mlで洗浄した。分液したエ
ーテル層を無水硫酸ナトリウムで乾燥後、減圧濃縮して
粗油１１０ｇを得た。これを精留し、２−メチル−１−
オキサスピロ（２.５）オクタン−２−カルボン酸メチ
ルエステル７９ｇ（沸点：１１７℃／１１mmHg、収率：
８６％）を得た。EXAMPLES Next, the present invention will be described more specifically by showing reference examples and examples. Reference Example 1 98 g of methyl 2-chloropropionate and 49 g of cyclohexanone were dissolved in 200 ml of ether and cooled to 0 ° C. Under a nitrogen stream, 45.5 g of sodium methoxide (95% powder) was gradually added. After completion of the reaction, the reaction mixture was washed with 200 ml of 0.5N hydrochloric acid aqueous solution. Then, it was washed with 100 ml of saturated sodium bicarbonate water and 200 ml of saturated saline water. The separated ether layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure to obtain 110 g of crude oil. This is rectified and 2-methyl-1-
79 g of oxaspiro (2.5) octane-2-carboxylic acid methyl ester (boiling point: 117 ° C./11 mmHg, yield:
86%).
【０００９】参考例２ エチル ２−クロロプロピオナート１０ｇとシクロヘキ
サノン７.２ｇをエーテル４０mlに溶解し、０℃に冷却
した。窒素気流下、ナトリウムエトキシド７.９ｇを徐
々に加えた。室温で１時間撹拌した後、１規定塩酸水溶
液２０mlで洗浄した。次いで、飽和重曹水１０mlと飽和
食塩水１００mlで洗浄した。分液したエーテル層を無水
硫酸ナトリウムで乾燥後、減圧濃縮して粗油８.１ｇを
得た。これを精留し、２−メチル−１−オキサスピロ
（２.５）オクタン−２−カルボン酸エチルエステル１.
４ｇ(沸点：８０〜８５℃／３mmHg、収率：３２％）を
得た。Reference Example 2 10 g of ethyl 2-chloropropionate and 7.2 g of cyclohexanone were dissolved in 40 ml of ether and cooled to 0 ° C. Under a nitrogen stream, 7.9 g of sodium ethoxide was gradually added. After stirring at room temperature for 1 hour, the mixture was washed with 20 ml of 1N aqueous hydrochloric acid solution. Then, it was washed with 10 ml of saturated sodium hydrogen carbonate solution and 100 ml of saturated saline solution. The separated ether layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 8.1 g of crude oil. This is rectified and 2-methyl-1-oxaspiro (2.5) octane-2-carboxylic acid ethyl ester 1.
4 g (boiling point: 80-85 ° C./3 mmHg, yield: 32%) was obtained.
【００１０】参考例３ メチルモノクロロアセトアセタート５０ｇとシクロヘキ
サノン４５ｇをエーテル１００mlに溶解し、−５℃に冷
却した。ナトリウムメトキシド（メタノール２８％溶
液）８９ｇを徐々に加えた。−５℃で１時間撹拌した
後、１０℃でさらに１時間撹拌した。反応後、エーテル
１００mlと水２００mlを加え、分液した。エーテル層を
飽和食塩水で洗浄後、無水硫酸マグネシウムで乾燥し
た。濾液を減圧濃縮し、粗油６５ｇを得た。これを精留
し、１−オキサスピロ（２.５）オクタン−２−カルボ
ン酸メチルエステル３８ｇ(沸点：８２℃／４mmHg、収
率：５４％）を得た。Reference Example 3 50 g of methyl monochloroacetoacetate and 45 g of cyclohexanone were dissolved in 100 ml of ether and cooled to -5 ° C. 89 g of sodium methoxide (28% methanol solution) was gradually added. After stirring at -5 ° C for 1 hour, the mixture was further stirred at 10 ° C for 1 hour. After the reaction, 100 ml of ether and 200 ml of water were added to separate the layers. The ether layer was washed with saturated saline and then dried over anhydrous magnesium sulfate. The filtrate was concentrated under reduced pressure to obtain 65 g of crude oil. This was rectified to obtain 38 g of 1-oxaspiro (2.5) octane-2-carboxylic acid methyl ester (boiling point: 82 ° C./4 mmHg, yield: 54%).
【００１１】実施例１ シャンプー用のベース香料として作成したトロピカルフ
ルーツベースに新たに２−メチル−１−オキサスピロ
（２.５）オクタン−２−カルボン酸メチルエステルを
５％添加した処方（Ａ）は、その代わりにジプロピレン
グリコールを添加した処方（Ｂ）に比べ、トップノート
のフルーティー感がマイルドになった。また、２−イソ
ブチル−５−メチルチアゾールと相まってトロピカルな
イメージをより強く感じさせた。Example 1 A formulation (A) was prepared by adding 5% of 2-methyl-1-oxaspiro (2.5) octane-2-carboxylic acid methyl ester to a tropical fruit base prepared as a base fragrance for shampoo. , Instead of the formula (B) in which dipropylene glycol was added, the fruity feeling of the top note became milder. In addition, the tropical image was more strongly felt in combination with 2-isobutyl-5-methylthiazole.
【００１２】[0012]
【表１】 [Table 1]
【００１３】実施例２ 液体芳香剤レモンライム調ベースに、新たに２−メチル
−１−オキサスピロ（２.５）オクタン−２−カルボン
酸エチルエステルを３％添加した処方（Ａ）は、その代
わりにジプロピレングリコールを添加した処方（Ｂ）に
比べ、爽やかさと柑橘が有する甘さが明確になった。こ
の明るさと甘さが嗜好性を増加させるのに寄与してい
る。Example 2 A liquid fragrance lemon lime-like base was newly added with 3% of 2-methyl-1-oxaspiro (2.5) octane-2-carboxylic acid ethyl ester. The freshness and the sweetness of citrus were clarified as compared with the formulation (B) in which dipropylene glycol was added to. This brightness and sweetness contributes to the increase in palatability.
【００１４】[0014]
【表２】 [Table 2]
【００１５】実施例３ シャンプー等のトイレタリー製品に使用されているアッ
プルベースに１−オキサスピロ（２.５）オクタン−２
−カルボン酸エチルエステルを５％添加した処方（Ａ）
は、ジプロピレングリコールのみを添加した処方（Ｂ）
に比べ、アップルの果肉感が増加し、よりナチュラルな
感じを呈した。Example 3 1-oxaspiro (2.5) octane-2 was added to the apple base used in toiletry products such as shampoos.
-Formulation (A) containing 5% of carboxylic acid ethyl ester
Is a formulation (B) containing only dipropylene glycol
Compared with, the flesh feeling of apple was increased, and a more natural feeling was exhibited.
【００１６】[0016]
【表３】 [Table 3]
【００１７】[0017]
【発明の効果】前記式（１）を有する１−オキサスピロ
（２.５）オクタン−２−カルボン酸エステルからなる
香料およびこれを含有する香料組成物は、トロピカルフ
ルーツ様の甘い香りを有し、香料組成物に添加すること
によってその香料組成物の甘さを強調し、全体をエキゾ
チックな香りとする。[Effects of the Invention] A fragrance comprising 1-oxaspiro (2.5) octane-2-carboxylic acid ester having the above formula (1) and a fragrance composition containing the same have a tropical fruit-like sweet odor, By adding to the fragrance composition, the sweetness of the fragrance composition is emphasized to make the whole fragrance exotic.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 和泉 健一郎 岡山県勝田郡勝央町太平台１−２ 小川香 料株式会社岡山研究所内 (72)発明者 亀田 弥 岡山県勝田郡勝央町太平台１−２ 小川香 料株式会社岡山研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenichiro Izumi Inventor, Tairadai 1-2, Shoo-cho, Katsuta-gun, Okayama Prefecture Ogawa Kaori Co., Ltd. Okayama Laboratory (72) Inventor Ya Kameda Taiheidai, Katsuta-cho, Katsuta-gun 1- 2 Ogawa Kaori Okayama Laboratory Co., Ltd.
Claims (2)
を示し、Ｒ2は炭素数１〜４のアルキル基を示す）で表
される１−オキサスピロ（２.５）オクタン−２−カル
ボン酸エステルからなる香料。1. A compound represented by the general formula (1): (In the formula, R 1 represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 2 represents an alkyl group having 1 to 4 carbon atoms.) 1-oxaspiro (2.5) octane-2- Fragrance made from carboxylic acid ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10526594A JPH07310089A (en) | 1994-05-19 | 1994-05-19 | Perfume comprising 1-oxaspiro(2. 5)octane-2-carboxylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10526594A JPH07310089A (en) | 1994-05-19 | 1994-05-19 | Perfume comprising 1-oxaspiro(2. 5)octane-2-carboxylic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07310089A true JPH07310089A (en) | 1995-11-28 |
Family
ID=14402836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10526594A Pending JPH07310089A (en) | 1994-05-19 | 1994-05-19 | Perfume comprising 1-oxaspiro(2. 5)octane-2-carboxylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07310089A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005108534A1 (en) * | 2004-05-07 | 2005-11-17 | Givaudan Sa | Alicyclic carboxylic acid oxycarbonylmethyl esters and their use as odorants |
| JP2007511624A (en) * | 2003-10-23 | 2007-05-10 | フイルメニツヒ ソシエテ アノニム | Spiro epoxy-macro ring as perfume ingredient |
-
1994
- 1994-05-19 JP JP10526594A patent/JPH07310089A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007511624A (en) * | 2003-10-23 | 2007-05-10 | フイルメニツヒ ソシエテ アノニム | Spiro epoxy-macro ring as perfume ingredient |
| JP4891775B2 (en) * | 2003-10-23 | 2012-03-07 | フイルメニツヒ ソシエテ アノニム | Spiro epoxy-macro ring as perfume ingredient |
| WO2005108534A1 (en) * | 2004-05-07 | 2005-11-17 | Givaudan Sa | Alicyclic carboxylic acid oxycarbonylmethyl esters and their use as odorants |
| JP2007536285A (en) * | 2004-05-07 | 2007-12-13 | ジボダン エス エー | Cycloaliphatic carboxylic acid oxycarbonylmethyl esters and their use as odorants |
| US7687452B2 (en) | 2004-05-07 | 2010-03-30 | Givaudan Sa | Organic compounds |
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