JPS6136819B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound having properties useful in perfumes and perfumes containing the same. More specifically, the present invention relates to a novel angelic acid ester represented by the following formula ().

Angelic acid is an unsaturated carboxylic acid represented by the structural formula () below. The official name is (Z)-2-methyl-2-butenoic acid. Some angelic acid esters are natural essential oils, such as chamomile oil.
It is widely known that it is important as a fragrance ingredient.

However, (Z)-3-hexenyl angelic acid represented by the above structural formula () is a new compound and has not been described in any literature available to date.

The present inventors discovered that when blending into a fragrance composition,
As a result of intensive research into compounds that are effective in modulating fragrance and enhancing aroma, especially in minute amounts, we have discovered that the compound represented by the formula () above is a compound that is effective for this purpose, and have arrived at the present invention.

Compound of the present invention, namely angelic acid (Z)-3
-The aroma of hexenyl has a strong green note and a rosy side, with a greenish sweetness of perilla. It is particularly effective in producing herbal notes, modern chypres, and floral bouquet green notes.

It has been found that the compounds of the invention, especially when added to other perfume compositions, significantly improve the aroma of particular perfume compositions.

It has become clear that this compound exhibits a wonderful effect when blended into a blended fragrance composition used particularly as a fragrance for cosmetics.

The compounds of the present invention can be added to cosmetics (soaps, ointments, powders, toothpastes, deodorants, shampoos, colognes, lotions, etc.), detergents, etc. and used as fragrance compositions (perfuming compositions). It can also be used as a flavor by adding it to luxury items and drinks.

As mentioned above, the compound of the present invention exhibits even better effects when used as a new fragrance composition by blending it with another fragrance composition. The amount to be blended varies depending on the purpose and the perfume composition to be blended, but generally it is preferably 0.005 to 50% by weight, more preferably 0.05 to 30% by weight of the total weight of the blended perfume composition. .

Typical formulation examples are shown in Examples, but the present invention is of course not limited thereto.

The compound of the present invention can be produced, for example, by the method described below.

That is, angelic acid methyl ester and the alcohol corresponding to the compound of the present invention, namely (Z)-3-
The desired angelic acid ester is obtained by treating the mixture with hexenyl alcohol in the presence of a transesterification catalyst.

Purification of the target compound can be carried out by conventional purification means such as rectification. According to rectification,
It is easy to separate the target compound from the alcohol as a raw material, methyl angelicate, and methanol as a by-product. The transesterification catalyst remains as a residue in the column during rectification, but it is preferable to distill off the volatile reaction mixture in a relatively short time by simple distillation or rectification using a column with a small number of plates before rectification. It is better to separate it from the catalyst by Thereafter, the target compound can be extracted in pure form by rectification.

Acids are generally used as transesterification catalysts, but metal compounds such as organotin compounds and titanium alkoxides are also suitably used. Any solvent may be used as long as it does not adversely affect the reaction, but generally a non-contactable solvent may be used. The compounds of the present invention are produced according to other commonly used transesterification conditions.

In the above production method, the reaction proceeds with better yield if a means is used to continuously remove by-produced methanol from the reaction mixture by distillation or adsorption onto a molecular sieve. One specific production example is shown in the following example, but the present invention is of course not limited thereto.

Example 1 Production of (Z)-3-hexenyl angelic acid A mixture of 20.0 g of methyl angelicate, 26.34 g of (Z)-3-hexenyl alcohol, 100 ml of toluene, and 1.2 g of diotatyltin laurate was placed in a 300 ml glass flask. Molecular sieve on top
Equipped with a Soxhlet extractor packed with 4A and a reflux condenser.

The mixture is heated and continuously refluxed so that the reflux liquid returns to the flask through the molecular sieve 4A. The mixture obtained by heating for a total of 26 hours was simply distilled at 120℃ (25mmHg).
33.10g of fraction was obtained. This was further subjected to rectification to obtain 8.46 g of a fraction at 115°C (22 mmHg). This compound was analyzed by gas chromatography (column; Silicon SE-52.2%/Chromosolve GHP)
The purity by area ratio was found to be 99.81% by analysis. The refractive index (D line, 20°C) was 1.456. In the infrared spectrum, 2870-3020, 1720,
1650, 1455, 1390, 1350, 1255, 1225, 1155,
It showed absorption at 1080, 1040, 845, and 760 cm ^-1 (liquid film).

In the proton nuclear magnetic resonance spectrum, δ
=0.97 (triplet, 3H), 1.8~2.2 (multiplet, 8H),
It showed absorption at 2.43 (quartet, 2H), 4.16 (triplet, 2H), 5.4 (multiplet, 2H), 6.06 (multiplet, 1H) (in deuterated chloroform, TMS internal standard).

Example 2 Green modern bouquet perfume composition Weight% Bergamotu oil 3.0 Lemon oil 2.0 Ylang ylang oil extra 1.0 Cis-3-hexenyl acetate 10% 0.5 Essence butuchuu 10% 0.2 Methylheptenone 0.3 Benzyl acetate 2.0 Phenylethyl alcohol 20.0 Citronellol 5.0 MPC Acetate 2.5 Hydroxycitronellal 4.0 Eugenol 2.0 α-Hexylcinnamaldehyde 6.0 Vetivan Acetate 15.0 Oakmoss Absolute 1.0 Perbalsam 1.0 Galbanum Oil 0.5 Iris Concrete 1.0 γ-Methyl Ionone 10.0 Benzyl Salicylate 8.0 Diyasmine Absolute 0.5 Ambergris 10% (alcohol) 0.5 Pentalide 3.0 Dipropylene glycol 10.0 Angelic acid (Z)-3-hexenyl 1.0 Total 100.0 The above fragrance composition was formulated with angelic acid (Z)-3-hexenyl by three experienced investigators. It was judged that the natural and fresh appeal was significantly increased and the fragrance tone was very good compared to the comparative composition without the fragrance.

Claims (1)

[Claims] 1 Formula () Angelic acid ester derivative 2 represented by formula () A fragrance composition containing an angelic acid ester derivative represented by: