JP3676394B2 - Fragrance composition - Google Patents
Fragrance composition Download PDFInfo
- Publication number
- JP3676394B2 JP3676394B2 JP12165094A JP12165094A JP3676394B2 JP 3676394 B2 JP3676394 B2 JP 3676394B2 JP 12165094 A JP12165094 A JP 12165094A JP 12165094 A JP12165094 A JP 12165094A JP 3676394 B2 JP3676394 B2 JP 3676394B2
- Authority
- JP
- Japan
- Prior art keywords
- ether
- fragrance
- methoxyphenethyl
- composition
- methyl ether
- 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 - Lifetime
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- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、調香素材として有用な新規エーテル化合物と、該化合物を含有する香料組成物に関する。
【０００２】
【従来の技術】
有機合成化学の進歩に伴い、香料として用い得る化合物は飛躍的に増加し、今やその数は３，０００種類とも５，０００種類とも言われている。それらの中でエーテル化合物は一般に香りの弱いものが多いため、香料として使用される化合物の種類は極僅かであるのが現状である。
【０００３】
現在広く香料として使用されているエーテル化合物として、まず脂肪族化合物では、森林調のセドリルメチルエーテル、カンファー様の１，８−シネオール等が知られている。一方芳香族化合物としては、アニス様のアネトールや、スパイシーなメチルチャビコール、メチルオイゲノール等が知られている。しかしこれらの化合物の香りからも判るように、一般にエーテル化合物の香りは、香料を調合する際に最も重要な要素とも言うべき、フローラル調並びにグリーン調に乏しいものが多い。また、特に構造中に二重結合等の不飽和結合を有する化合物の場合には、化学的に安定とされるエーテル化合物の特性が発揮されず、不飽和結合に対するハロゲンや水の付加反応、置換反応、更には不飽和結合の重合反応等が起こる可能性があり、化合物本来の香気が損なわれる可能性が高い。
【０００４】
【発明が解決しようとする課題】
そこで上記実状に鑑み、本発明の目的はフローラル調並びにグリーン調の持続性のある香気を持ち、更には、安定性にも優れた香料素材を提供することにある。
【０００５】
【課題を解決するための手段】
本発明者らは、新規調香素材の開発を目的に種々の植物の香気成分を探索する中で、地中海沿岸地方及び西南アジア原産のムスカリ・アルメニアクム（Ｍｕｓｃａｒｉ ａｒｍｅｎｉａｃｕｍ Ｌｅｉｃｈｔｌ．ｅｘ Ｂａｋ．）の持続性のある強い個性的な香りに注目し、その成分研究を行った。その結果、この花精油の主成分として、下記式（ＩＩ）
【０００６】
【化３】
で表される、４−メトキシフェネチルメチルエーテルを発見し、さらなる検討を続け本発明に到達した。
【０００８】
本発明は下記式（Ｉ）
【０００９】
【化４】
式中ｎは１又は２、Ｒ１はＣＨ３、Ｃ２Ｈ５又はＣ３Ｈ７、Ｒ２はＣＨ３又はＣ２Ｈ５を示す、
で表わされるエーテル化合物を含有する香料組成物を提供するものである。
【００１１】
本発明のエーテル化合物はフローラルないしグリーン調の香気を有し新規調香素材として有用である。
【００１２】
本発明のエーテル化合物は４−メトキシベンジルアルコールや４−メトキシフェネチルアルコール等の市販の化合物を用い単品として合成できる。
【００１３】
以下に本発明のエーテル化合物の香気特性及びＩＲ、ＭＳデータを示す。
【００１４】
【表１】
【表２】
【表３】
【表４】
【表５】
【表６】
【表７】
【表８】
【表９】
【表１０】
【表１１】
【表１２】
本発明のエーテル化合物は、香水、オーデコロン、シャンプー、リンス、化粧水、石鹸、洗剤、芳香剤、入浴剤等に使用する香料組成物に配合し、優れた官能特性及び安定性を持った製品にすることができる。
【００２７】
本発明のエーテル化合物を香料組成物の製造に使用する場合、その配合量は通常０．１〜３０重量％の範囲で選択されるが、意図する官能効果によってはこの範囲外でも使用しうる。本発明のエーテル化合物を配合すべき香料組成物は特に限定されず上記用途等に通常使用されている調合香料組成物等適宜のものを用いうる。
【００２８】
次に合成例及び実施例を挙げて本発明を更に詳細に説明するが、本発明は、これにより限定されるものではない。
【００２９】
【実施例】
合成例１ ４−メトキシベンジルメチルエーテルの合成
４−メトキシベンジルアルコール６ｇ（０．０４３ｍｏｌ）を、Ｎ，Ｎ−ジメチルホルムアミド８０ｍｌに溶解し、金属ナトリウム１．９７８ｇ（０．０８６ｇ・ａｔｍ．）を加え室温で１時間３０分攪拌した。反応後、ヨウ化メチル９．１５９ｇ（０．０６４ｍｏｌ）を、Ｎ，Ｎ−ジメチルホルムアミド４０ｍｌで溶解したものを滴下し、室温で５時間攪拌し、反応後ジエチルエーテルを加え飽和食塩水で洗浄した後、エーテル層を減圧回収することにより、粗生成物４．２７６ｇを得た。更に、粗生成物を精製して４−メトキシベンジルメチルエーテル１．９６１ｇを得た。（収率３０．０ｍｏｌ％）構造はＩＲ、ＭＳにより確認した。
【００３０】
合成例２ ４−メトキシフェネチルメチルエーテルの合成
４−メトキシフェネチルアルコール１０ｇ（０．０６６ｍｏｌ）を、Ｎ，Ｎ−ジメチルホルムアミド１５０ｍｌに溶解し、金属ナトリウム２．２７０ｇ（０．０９９ｇ・ａｔｍ．）を加え室温で１時間３０分攪拌した。反応後、ヨウ化メチル１４．０２０ｇ（０．０９９ｍｏｌ）を、Ｎ，Ｎ−ジメチルホルムアミド５０ｍｌで溶解したものを滴下し、室温で５時間攪拌し、反応後ジエチルエーテルを加え飽和食塩水で洗浄した後、エーテル層を減圧回収することにより、粗生成物６．５３０ｇを得た。更に、粗生成物を精製して４−メトキシフェネチルメチルエーテル２．８６０ｇを得た。（収率２６．１０ｍｏｌ％）構造はＩＲ、ＭＳにより確認した。
【００３１】
実施例１ カーネーションタイプの調合香料組成物として下記の各成分を混合した。
【００３２】
実施例２ ナチュラルローズタイプの調合香料組成物として下記の各成分を混合した。
【００３３】
実施例３ ヒヤシンスタイプの調合香料組成物として下記の各成分を混合した。
【００３４】
【発明の効果】
本発明のメトキシフェニル及びエトキシフェニル基を有するエーテル類と、それらを含有する香料組成物は、香料素材として好ましい効果を与える優れた素材であるとともに、その香料組成物は従来得る事の出来なかった個性ある香りである。
【図面の簡単な説明】
【図１】２−メトキシフェニルエチルメチルエーテルのＭＳスペクトル図。
【図２】３−メトキシフェネチルメチルエーテルのＭＳスペクトル図。
【図３】４−メトキシフェネチルメチルエーテルのＭＳスペクトル図。
【図４】２−メトキシフェネチルエチルエーテルのＭＳスペクトル図。
【図５】３−メトキシフェネチルエチルエーテルのＭＳスペクトル図。
【図６】４−メトキシフェネチルエチルエーテルのＭＳスペクトル図。
【図７】４−メトキシフェネチルメチルエーテルのＩＲスペクトル図。[0001]
[Industrial application fields]
The present invention relates to a novel ether compound useful as a fragrance material and a fragrance composition containing the compound.
[0002]
[Prior art]
With the progress of organic synthetic chemistry, the compounds that can be used as perfumes have increased dramatically, and now the number is said to be 3,000 or 5,000. Among them, ether compounds generally have a weak fragrance, and therefore there are very few types of compounds used as perfumes.
[0003]
As ether compounds that are currently widely used as fragrances, forest-like cedryl methyl ether, camphor-like 1,8-cineole and the like are known as aliphatic compounds. On the other hand, as an aromatic compound, anise-like anethole, spicy methylchavicol, methyleugenol, and the like are known. However, as can be seen from the scents of these compounds, generally, the scents of ether compounds are often poor in floral tone and green tone, which should be said to be the most important factor in the preparation of fragrances. In particular, in the case of a compound having an unsaturated bond such as a double bond in the structure, the characteristics of the chemically stable ether compound are not exhibited, and an addition reaction or substitution of halogen or water to the unsaturated bond There is a possibility that a reaction, a polymerization reaction of an unsaturated bond, and the like occur, and the original aroma of the compound is likely to be impaired.
[0004]
[Problems to be solved by the invention]
Then, in view of the above-mentioned actual situation, an object of the present invention is to provide a perfume material having a floral-like and green-like scent and having excellent stability.
[0005]
[Means for Solving the Problems]
In the search for aroma components of various plants for the purpose of developing a new scented material, the present inventors have continued the Muscari armeniacum Leichtl. Ex Bak. Focusing on the strong and unique fragrance, we researched its ingredients. As a result, as a main component of this flower essential oil, the following formula (II)
[0006]
[Chemical 3]
4-methoxyphenethyl methyl ether represented by the following formula was discovered, and further studies were continued to arrive at the present invention.
[0008]
The present invention relates to the following formula (I)
[0009]
[Formula 4]
In the formula, n is 1 or 2, R 1 is CH 3 , C 2 H 5 or C 3 H 7 , R 2 is CH 3 or C 2 H 5 ,
The fragrance | flavor composition containing the ether compound represented by this is provided.
[0011]
The ether compound of the present invention has a floral or green fragrance and is useful as a novel fragrance material.
[0012]
The ether compound of the present invention can be synthesized as a single product using commercially available compounds such as 4-methoxybenzyl alcohol and 4-methoxyphenethyl alcohol.
[0013]
The aroma characteristics, IR and MS data of the ether compound of the present invention are shown below.
[0014]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
[Table 6]
[Table 7]
[Table 8]
[Table 9]
[Table 10]
[Table 11]
[Table 12]
The ether compound of the present invention is blended in a perfume composition used for perfume, eau de cologne, shampoo, rinse, lotion, soap, detergent, fragrance, bathing agent, etc., to produce a product having excellent sensory characteristics and stability. can do.
[0027]
When using the ether compound of this invention for manufacture of a fragrance | flavor composition, the compounding quantity is normally selected in the range of 0.1 to 30 weight%, but depending on the intended sensory effect, it can be used outside this range. The perfume composition to which the ether compound of the present invention is to be blended is not particularly limited, and appropriate ones such as a blended perfume composition usually used for the above-mentioned uses and the like can be used.
[0028]
Next, although a synthesis example and an Example are given and this invention is demonstrated still in detail, this invention is not limited by this.
[0029]
【Example】
Synthesis Example 1 Synthesis of 4-methoxybenzyl methyl ether 6 g (0.043 mol) of 4-methoxybenzyl alcohol was dissolved in 80 ml of N, N-dimethylformamide, and 1.978 g (0.086 g · atm.) Of metallic sodium was added. Stir at room temperature for 1 hour 30 minutes. After the reaction, 9.159 g (0.064 mol) of methyl iodide dissolved in 40 ml of N, N-dimethylformamide was added dropwise and stirred at room temperature for 5 hours. After the reaction, diethyl ether was added and washed with saturated brine. Thereafter, the ether layer was recovered under reduced pressure to obtain 4.276 g of a crude product. Further, the crude product was purified to obtain 1.961 g of 4-methoxybenzyl methyl ether. (Yield 30.0 mol%) The structure was confirmed by IR and MS.
[0030]
Synthesis Example 2 Synthesis of 4-methoxyphenethyl methyl ether 10 g (0.066 mol) of 4-methoxyphenethyl alcohol was dissolved in 150 ml of N, N-dimethylformamide, and 2.270 g of metal sodium (0.099 g · atm.) Was added. Stir at room temperature for 1 hour 30 minutes. After the reaction, methyl iodide (14.020 g, 0.099 mol) dissolved in N, N-dimethylformamide (50 ml) was added dropwise and stirred at room temperature for 5 hours. After the reaction, diethyl ether was added and washed with saturated brine. Thereafter, the ether layer was recovered under reduced pressure to obtain 6.530 g of a crude product. Further, the crude product was purified to obtain 2.860 g of 4-methoxyphenethyl methyl ether. (Yield 26.10 mol%) The structure was confirmed by IR and MS.
[0031]
Example 1 The following components were mixed as a carnation-type blended fragrance composition.
[0032]
Example 2 The following components were mixed as a natural rose type blended fragrance composition.
[0033]
Example 3 The following components were mixed as a hyacinth type blended fragrance composition.
[0034]
【The invention's effect】
The ethers having methoxyphenyl and ethoxyphenyl groups of the present invention and the fragrance composition containing them are excellent materials that give a preferable effect as a fragrance material, and the fragrance composition could not be obtained conventionally. It has a unique scent.
[Brief description of the drawings]
FIG. 1 is an MS spectrum of 2-methoxyphenylethyl methyl ether.
FIG. 2 is an MS spectrum of 3-methoxyphenethyl methyl ether.
FIG. 3 is an MS spectrum of 4-methoxyphenethyl methyl ether.
FIG. 4 is an MS spectrum of 2-methoxyphenethyl ethyl ether.
FIG. 5 is an MS spectrum of 3-methoxyphenethyl ethyl ether.
FIG. 6 is an MS spectrum of 4-methoxyphenethyl ethyl ether.
FIG. 7 is an IR spectrum of 4-methoxyphenethyl methyl ether.
Claims (1)
で表わされるエーテル化合物を含有する香料組成物。Formula (I)
The fragrance | flavor composition containing the ether compound represented by these.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12165094A JP3676394B2 (en) | 1994-04-25 | 1994-04-25 | Fragrance composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12165094A JP3676394B2 (en) | 1994-04-25 | 1994-04-25 | Fragrance composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004334384A Division JP2005089473A (en) | 2004-11-18 | 2004-11-18 | Ether compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07291883A JPH07291883A (en) | 1995-11-07 |
| JP3676394B2 true JP3676394B2 (en) | 2005-07-27 |
Family
ID=14816506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12165094A Expired - Lifetime JP3676394B2 (en) | 1994-04-25 | 1994-04-25 | Fragrance composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3676394B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1269982A1 (en) | 2001-06-30 | 2003-01-02 | Givaudan SA | Fragrance and flavour compositions |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3128987A1 (en) * | 1981-07-22 | 1983-02-10 | Dragoco Gerberding & Co Gmbh, 3450 Holzminden | USE OF 1-ETHOXI-4-ETHYL-BENZOL AS A SMELLING AND FLAVORING SUBSTANCE |
| US4657700A (en) * | 1983-10-07 | 1987-04-14 | Givaudan Corporation | Fragrance compositions containing benzyl ethers |
| CA1274851A (en) * | 1984-08-01 | 1990-10-02 | Eugene G. Harris | 4-alkylphenyl-2-alkoxyethyl ethers and fragrance compositions containing same |
| JPH0694417B2 (en) * | 1984-08-03 | 1994-11-24 | 株式会社資生堂 | Hyundai rose flavor composition and method for producing the same |
| DE3913163A1 (en) * | 1989-04-21 | 1990-10-25 | Basf Ag | METHOD FOR PRODUCING BENZYL METHYL ETHER |
| JP2835779B2 (en) * | 1990-11-17 | 1998-12-14 | 鐘淵化学工業株式会社 | Method for producing isobutylene-based polymer having functional end |
| WO1995000467A1 (en) * | 1993-06-24 | 1995-01-05 | Hoechst Celanese Corporation | Process for preparing phenethanol ethers |
-
1994
- 1994-04-25 JP JP12165094A patent/JP3676394B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07291883A (en) | 1995-11-07 |
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