JPS5940393B2 - Macrocyclic diesters and fragrances containing them - Google Patents
Macrocyclic diesters and fragrances containing themInfo
- Publication number
- JPS5940393B2 JPS5940393B2 JP54126879A JP12687979A JPS5940393B2 JP S5940393 B2 JPS5940393 B2 JP S5940393B2 JP 54126879 A JP54126879 A JP 54126879A JP 12687979 A JP12687979 A JP 12687979A JP S5940393 B2 JPS5940393 B2 JP S5940393B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- dioxa
- fragrance
- methyl
- compound
- 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
Landscapes
- Cosmetics (AREA)
- Fats And Perfumes (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Description
【発明の詳細な説明】
本発明は香料に有用な性質を有する新規な化合物とそれ
らを含む香料に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel compounds having properties useful in perfumes and perfumes containing them.
大環状ケトン、大環状ラクトン、大環状ジエステルなど
の内のあるものが、香料成分として重要であることは広
く知られている。大環状ジエステスでは２・５−ジオキ
サー１・ ６−ジオキソシクロヘプタデカンおよび２
・ ５−ジオキサー１・ ６−ジオキソシクロヘキサデ
カンがムスク系香料として著名であり、広く香料の調合
に使用されている。しかしながら、側鎖のついた大環状
ジエステルは、香料成分としては全く知られていない。
本発明者らは香料組成物に配合する場合に、特に微量で
香料の変調および香気の増強に効果のある化合物を鋭意
検討した結果、側鎖を有する新規な環状ジエステルであ
る下記一般式（Ｉ）の化合物がこの目的に効果のある化
合物であることを見出し本発明に到達した。It is widely known that certain macrocyclic ketones, macrocyclic lactones, macrocyclic diesters, etc. are important as fragrance ingredients. In the macrocyclic dieestes, 2,5-dioxor 1,6-dioxocycloheptadecane and 2
- 5-Dioxer 1.6-dioxocyclohexadecane is well-known as a musk fragrance and is widely used in the preparation of fragrances. However, macrocyclic diesters with side chains are completely unknown as fragrance ingredients.
The present inventors conducted intensive studies on compounds that are effective in modulating fragrances and enhancing aroma when incorporated into fragrance compositions, especially in small amounts. As a result, the present inventors found that the following general formula (I ) was found to be a compound effective for this purpose, and the present invention was achieved.
０＝Ｃ−（ＣＨ２）ｉ０−Ｃ＝０
Ｏ−ＣＨ−（ＣＨ２）ｎ−Ｏ（Ｉ）
（ただしｎはｌまたは２を示す）
一般式（Ｉ）の本発明化合物のうち、ｎが１のものは３
−メチルー ２ ・ ５−ジオキサー１・ ６−ジオキ
ソシクロヘキサデカンであり、ｎが２のものは３−メチ
ルー ２ ・ ６−ジオキサー１・ ７−ジオキソシク
ロヘプタデカンである。0=C-(CH2)i0-C=0 O-CH-(CH2)n-O(I) (However, n represents 1 or 2) Among the compounds of the present invention of general formula (I), n is 1 The one is 3
-Methyl-2.5-dioxar 1.6-dioxocyclohexadecane, and when n is 2, it is 3-methyl-2.6-dioxar 1.7-dioxocycloheptadecane.
一般式（ハを有する本発明化合物はいずれも淡いジヤ香
様香気に特徴を有する化合物であるが、特に注目すべき
香気を有するものではない。All of the compounds of the present invention having the general formula (C) are characterized by a light jacquard-like aroma, but they do not have a particularly noteworthy aroma.
しかし、・ 予想に反して本物質を他の香料組成物に微
量添加した場合、単一の化合物からは想像できない効果
を示し、その香料組成物の香気を大きく改善するへこと
が明らかとなつた。However, contrary to expectations, it has become clear that when this substance is added in small amounts to other fragrance compositions, it exhibits effects that could not be expected from a single compound, greatly improving the aroma of the fragrance composition. .
特に香粧用香料として使用される調合香料組成物に配合
すると素晴らしい効果を発揮する化合物であることが明
らかとなつた。本発明化合物はたとえば次の如く製造さ
れる。It has become clear that this compound exhibits excellent effects especially when incorporated into blended fragrance compositions used as fragrances for cosmetics. The compound of the present invention can be produced, for example, as follows.
すなわち、まず、ドデカン２酸またはそのジエステルと
プロピレングリコール（一般式（１）においてｎ−１の
場合）あるいはブチレングリコール（一般式（１）にお
いてｎ−２の場合）を重縮合させ、高分子重合体をつく
り、ついで触媒の存在下、高真空下で、直接あるいは溶
媒の存在下で、高温において解重合する。ここで用いら
れる触媒、溶媒などは、特に２・５−ジオキサ−１・６
−ジオキソシクロヘプタデカンなどについてよく知られ
ている解重合法に準じれば良い。しかしながら、本発明
の化合物の場合、側鎖があるからか、高温において解重
合反応中、特に分解反応を起しやすく、したがつて溶媒
を使用して反応温度を低くする方が望ましい。本化合物
は解重合後、洗浄、精留などの常法により香料成分とし
て十分な純度まで精製される。３−メチル−２・５−ジ
オキサ−１・６−ジオキソシクロヘキサデカン（一般式
（１）においてｎ−１の化合物）は、沸点１５３〜４℃
／２ｍｍＨｇ．Ｎ智−１．４５７９を示し常温で液体で
ある。That is, first, dodecane diic acid or its diester and propylene glycol (in the case of n-1 in general formula (1)) or butylene glycol (in the case of n-2 in general formula (1)) are polycondensed to form a polymer polymer. Coalescence is formed and then depolymerized in the presence of a catalyst under high vacuum, either directly or in the presence of a solvent, at elevated temperatures. The catalyst, solvent, etc. used here are particularly 2,5-dioxa-1,6
- The well-known depolymerization method for dioxocycloheptadecane etc. may be followed. However, in the case of the compound of the present invention, probably because of the presence of side chains, decomposition reactions are particularly likely to occur during the depolymerization reaction at high temperatures, and therefore it is preferable to use a solvent to lower the reaction temperature. After depolymerization, this compound is purified to a purity sufficient for use as a fragrance ingredient by conventional methods such as washing and rectification. 3-Methyl-2,5-dioxa-1,6-dioxocyclohexadecane (compound n-1 in general formula (1)) has a boiling point of 153 to 4°C.
/2mmHg. It shows N-1.4579 and is liquid at room temperature.
また、３−メチル−２・６−ジオキサ−１・７ジオキソ
シクロヘプタデカン（一般式（１）においてｎ−２の化
合物）は、沸点１５３〜４℃／２ｍＴ１ＬＨ８、Ｎ青−
１．４５７９を示し常温で液体である。本発明の化合物
は前述したようにジヤ香様香気を有するが、該化合物を
調合香料組成物に少量添加すると、それらの特徴ある芳
香を調和させると共にジャ香様香気が強調されて該化合
物を配合しない組成物より香気が大きく改善され、更に
保留性も増大する。特にフローラルブーケ、シプレ、ラ
ベーダ一、バイオレツトなどのタイプの調合香料組成物
に添加すると効果が大きい。本発明の香料に使用される
３−メチル−２・５ジオキサ−１・６−ジオキソシクロ
ヘキサデカンまたは３−メチル−２・６−ジオキサ−１
・７ジオキソシクロヘプタデカンの配合量は、その目的
および配合される香料組成物によつて変えられるが、一
般には、香料組成物総重量の０．００５〜５０重量％が
望ましく、より好ましくは０．０５〜３０重量％が望ま
しい。In addition, 3-methyl-2,6-dioxa-1,7 dioxocycloheptadecane (compound n-2 in general formula (1)) has a boiling point of 153 to 4°C/2mT1LH8, N blue-
1.4579 and is liquid at room temperature. As mentioned above, the compound of the present invention has a jacquard-like aroma, and when the compound is added in a small amount to a blended fragrance composition, the characteristic aromas are harmonized and the jacquard-like odor is emphasized. The aroma is greatly improved compared to compositions without it, and the retention property is also increased. It is particularly effective when added to blended fragrance compositions of types such as floral bouquet, chypre, lavéda, and violet. 3-Methyl-2,5-dioxa-1,6-dioxocyclohexadecane or 3-methyl-2,6-dioxa-1 used in the fragrance of the present invention
- The amount of 7-dioxocycloheptadecane to be blended varies depending on the purpose and the perfume composition to be blended, but in general, 0.005 to 50% by weight of the total weight of the perfume composition is desirable, and more preferably 0.05 to 30% by weight is desirable.
次の実施例は本発明を具体的に説明するものであるが、
本発明はこれに限定されるものではない。The following examples specifically illustrate the invention:
The present invention is not limited to this.
実施例 １３−メチル−２・５−ジオキサ−１・６−ジ
オキソシクロヘキサデカンの製造ドデカン２酸１５０部
にプロピレングリコール１００部を加え、攪拌しながら
１８０〜２２『Ｃに加温すると水２１部が留出し、過剰
プロピレングリコールと重合物の混合物２２９部が生成
する。Example 1 Production of 3-methyl-2,5-dioxa-1,6-dioxocyclohexadecane 100 parts of propylene glycol was added to 150 parts of dodecanedioic acid and heated to 180-22°C with stirring, resulting in 21 parts of water. is distilled off, producing 229 parts of a mixture of excess propylene glycol and polymer.
この混合物１０２部に溶媒流動パラフイン４００部、触
媒ジオクチルスズラウレート８．１部を加え、１６０〜
２６０℃／２ｍｍＨｇで反応させると、過剰プロピレン
グリコール２１部、３−メチル−２・５−ジオキサ−１
・６−ジオキソシクロヘキサデカン５６部（純度８４％
）が得られる。原料ドデカン２酸よりの収率は５８％で
あつた。この反応液を常法により精製し、純粋な３−メ
チル−２・５−ジオキサ−１・６−ジオキソシクロヘキ
サデカンを得た。実施例 ２
３−メチル−２・６−ジオキサ−１・７ージオキソシク
ロヘプタデカンの製造ドデカン２酸１５０部にプチレン
グリコール１０５．７部を加え、攪拌しながら１８０〜
２２０℃に加温すると水２０．５部が留出し、過剰ブチ
レングリコールと重合物の混合物２３５，２部が生成す
る。To 102 parts of this mixture, 400 parts of solvent liquid paraffin and 8.1 parts of catalyst dioctyltin laurate were added.
When reacted at 260°C/2mmHg, 21 parts of excess propylene glycol, 3-methyl-2,5-dioxa-1
・56 parts of 6-dioxocyclohexadecane (purity 84%
) is obtained. The yield from the raw material dodecanedioic acid was 58%. This reaction solution was purified by a conventional method to obtain pure 3-methyl-2,5-dioxa-1,6-dioxocyclohexadecane. Example 2 Production of 3-methyl-2,6-dioxa-1,7-dioxocycloheptadecane 105.7 parts of butylene glycol was added to 150 parts of dodecanedioic acid, and while stirring, the
When heated to 220° C., 20.5 parts of water is distilled out and 235.2 parts of a mixture of excess butylene glycol and polymer are produced.
この混合物１００部に溶媒として流動パラフイン４００
部、触媒としてジオクチルスズラウレート１１部を加え
１６０〜２６０℃／２ｍｍＨｇで反応させると、過剰ブ
チレングリコール１９．４部、３−メチル−２・６−ジ
オキサ−１・７ージオキソシクロヘプタデカン５５．６
部（純度７４．５％）が得られる。原料ドデカン２酸よ
りの収率は４７％であつた。この反応液を常法により精
製し、純粋な３−メチル−２・６−ジオキサ−１・７ジ
オキソシクロヘプタデカンを得た。実施例 ３
フローラルブーケ調香料組成物
重量パーセント
ローズコンパウンド １５ムゲツトコ
ンパウンド ３５ライラツクコンパウンド
１９本香料組成物は３人の香料技術熟練
者により３メチル−２・５−ジオキサ−１・６−ジオキ
ソシクロヘキサデカンを配合しない比較組成物に比して
、その調子、保香性の点で著しく優れていると判定され
た。Add 400 parts of liquid paraffin as a solvent to 100 parts of this mixture.
When 11 parts of dioctyltin laurate was added as a catalyst and the reaction was carried out at 160-260°C/2 mmHg, 19.4 parts of excess butylene glycol and 3-methyl-2,6-dioxa-1,7-dioxocycloheptadecane were produced. 55.6
(purity 74.5%) is obtained. The yield from the raw material dodecanedioic acid was 47%. This reaction solution was purified by a conventional method to obtain pure 3-methyl-2,6-dioxa-1,7 dioxocycloheptadecane. Example 3 Floral Bouquet Perfume Composition Weight Percent Rose Compound 15 Mugett Compound 35 Lilac Compound
19 This fragrance composition was evaluated by three experts in fragrance technology in terms of tone and fragrance retention compared to a comparative composition that does not contain 3-methyl-2,5-dioxa-1,6-dioxocyclohexadecane. was judged to be significantly superior.
実施例 ４
シプレ調香料組成物
本香料組成物は３人の香料技術熟練者により３メチル−
２・５−ジオキサ−１・６−ジオキソシクロヘキサデカ
ンを配合しない比較組成物に比して、その調子、保香性
の点で著しく優れていると判定された。Example 4 Chypre perfume composition This perfume composition was prepared by three people skilled in perfumery technology.
It was determined that the composition was significantly superior in tone and fragrance retention compared to a comparative composition that did not contain 2,5-dioxa-1,6-dioxocyclohexadecane.
実施例 ５
フローラルブーケ調香料組成物
本香料組成物は３人の香料技術熟練者により３メチル−
２・６−ジオキサ−１・７ージオキソシクロヘプタデカ
ンを配合しない比較組成物に比して、その調子、保香性
の点で著しく優れていると判定された。Example 5 Floral Bouquet Perfume Composition This perfume composition was prepared by three 3-methyl perfumery experts.
It was judged that the composition was significantly superior in tone and fragrance retention compared to a comparative composition that did not contain 2,6-dioxa-1,7-dioxocycloheptadecane.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54126879A JPS5940393B2 (en) | 1979-10-03 | 1979-10-03 | Macrocyclic diesters and fragrances containing them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54126879A JPS5940393B2 (en) | 1979-10-03 | 1979-10-03 | Macrocyclic diesters and fragrances containing them |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5651472A JPS5651472A (en) | 1981-05-09 |
| JPS5940393B2 true JPS5940393B2 (en) | 1984-09-29 |
Family
ID=14946099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP54126879A Expired JPS5940393B2 (en) | 1979-10-03 | 1979-10-03 | Macrocyclic diesters and fragrances containing them |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5940393B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5955881A (en) * | 1982-09-22 | 1984-03-31 | Daicel Chem Ind Ltd | Macrocyclic diester and perfumery composition containing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2547267C3 (en) * | 1975-10-22 | 1979-05-03 | Chemische Werke Huels Ag, 4370 Marl | Process for the preparation of cyclic diesters of dodecanedioic acid |
| JPS5356681A (en) * | 1976-10-29 | 1978-05-23 | Toray Ind Inc | Preparation of macro ring ethylene dioates |
| US4165321A (en) * | 1977-09-21 | 1979-08-21 | Harris Eugene G | Process for the production of heterocyclic compounds |
-
1979
- 1979-10-03 JP JP54126879A patent/JPS5940393B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5651472A (en) | 1981-05-09 |
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