JPS5948412A - Woody perfume composition - Google Patents

Abstract

PURPOSE:The titled composition, containing a norbornane derivative and an oil- soluble component contained in a plant of plant of the genus Santalum of the family Santalaceae, and capable of improving the stability to the oxidation, light and heat of the norbornane derivative and further the perfume tone thereof. CONSTITUTION:A woody perfume composition containing a norbornane derivative of formula I or II (R1 and R2 are H, 1-4C aliphatic hydrocarbon residue or phenyl; R3 and R4 are H or CH3; R5 is 2-3C alkyl, alkenyl or alkylidene; the dotted line part represents a single or double bond in the C-C bond) and 0.5- 20wt%, preferably 1-15wt%, oil-soluble component contained in a plant belonging to the genus Santalum of the family Santalaceae. The norbornane derivative has improved woody aroma, e.g. the green, vetiver or sandalwood tone, but the additon of the above-mentioned oil-soluble component enhances fully the stability thereof and imparts the integrated elegant aroma thereto. Thus, the commodity value thereof can be improved.

Description

[Detailed description of the invention] The present invention relates to stabilized wood-based fragrance compositions.

In general, many synthetic fragrances change their scent when left in the air for a long time or when exposed to light.

For this purpose, antioxidants are sometimes added, but
Addition of antioxidants often changes the aroma, which is considered undesirable.

The present inventors conducted various studies aimed at improving the oxidative stability, photostability, and thermal stability of norbornane derivatives, which are synthetic fragrances, as well as improving their fragrance notes. As a result, they found that they were stabilized and The present invention was completed by discovering a formulation with improved fragrance tone.

That is, the present invention provides at least one norbornane derivative i'' selected from the group consisting of compounds represented by the following formulas (1) and (II) by adding 0.0% of an oil-soluble component contained in a plant of the genus Zhudenaceae to the at least one norbornane derivative i'' selected from the group consisting of compounds represented by the following formulas (1) and (II). The present invention relates to a stabilized woody fragrance composition characterized in that it contains 5 to 20% by weight.

I-In descriptions (1) and (II), R1 and R
2 is the same or different hydrogen atom, the number of carbon atoms is 1 to 4
represents an aliphatic hydrocarbon residue or a phenyl group,
R3 and R4 are all hydrogen atoms or methyl groups,
R5... is an alkyl group, alkenyl group, or alkylidene group having 2 to 3 carbon atoms, and == indicates that the carbon-carbon bond is a diagonal bond or a double bond, Further, the two = in the condensed 5M FJ of formula (n) also indicate that the carbon-carbon bond is a single bond or a double bond, but both bonds do not become a double bond at the same time.

Particularly preferred norbornane derivatives in the present invention are those selected from the group consisting of compounds represented by the following formulas (R1) and (IV).

H Here, the definitions of the symbols in both formulas are as follows: except that R1 is a methyl group or an ethyl group, the symbols in the above formulas (1) and (n)
The symbols are the same as each other.

The structural formulas (stereoisomers are not distinguished), names, aromas, and boiling points of representative norbornane derivatives are shown in Table 1 below.

For example, the norbornane derivatives of Tonot et al.
= No. 29189, No. 56-131744, and No. 56-116949.

The plants of the genus Zantulaceae as used in the present invention refer to root-parasitic plants of the genus Zantalum, which is a plant of the genus Zantulaceae and plants of the genus Cannabis. Alpum (Indian sandalwood, Indonesian white lu '4), Zandarum cunningami and Newland sandalwood), Zantalum austro caledonicum (Homei sandalwood, Ni-Caledonian white J, Sannorum freissinetianum (Hawaiian white sandalwood) Varieties include Xantarum ellipticum and Sannorum gunikiratum), Xantarum palm (Fino sandalwood),
Insulare (Insulare sandalwood), Xantarum miltifolium (Miltifolium sandalwood), Xantarum boninense (Muni White In), Sannorum lanceolasom (
(Australian sandalwood), Sannorum eucarya spicata (Western Australian sandalwood), Xantalum pleisianum (South Australian white J, Sada),
It refers to single or 1d mixtures of Onoris tenuihoria (East African sandalwood), Sannorum acuminatum, Xanthalum giginorum, Sannorum zell/calum, Sannorum birlarium, Sannorum haleakalae, Xanthalum ntrinum, etc. However, West Indian white] 1・″
・Tangerine Avaris genus T from the Caribbean Islands, commonly known as 1
[Six substances such as Amyris and Gursamifuera are excluded.]

Among these, the industrially important ones (d. Zantalum album, which is produced from Southeast Asia to India, and the white 1v'i from Mysore, India, is of particularly good quality, as well as Sannorum aust TJ caledonicum, → ]−
Xantalum lanceolanom and Xantalum eucarya sucata are suitable as raw materials for the present invention.

The oil-soluble components contained in these plants of the genus Sandulinae are: 4)/! It refers to the lignin contained in the woody parts of objects, and the essential oil, Shirakao oil, alone or in combination. Xantarene, Zanota's Coal, Santaral, Tele→Nonchlor, Teresantarnic acid, Nortrinchlor, Zantalal, Epi-Zantarene, Tol contained in the oil
) Sochroecazal Talolactone, Ehisantalol, Lanceol, Nu/Ferrol, Pizza YJ? It also refers to one or a mixture of noterzene-based compounds such as ren, oquinohydroeremophilin, etc.

The norbornane derivatives used in the compositions of the present invention generally have excellent woody aromas such as a green fresh woody scent, a vetiver woody scent, a sandalwood, white woody scent, and a sweet sandalwood scent. However, because it is an alcohol with a special structure, it is difficult to say that the oxidation stability, photostability, or thermal stability is sufficient in the chemically purified state of each alcohol, and it may not have the same old aroma. May lack maturity.

In order to improve these points, the present inventors added various phenolic additives, amine additives, and power/l.

We have been conducting research to improve the commercial value of compound-based additives having a bonyl group, or all-norbornane derivatives of various natural oils and fats.

As a result, 0.5
It has been discovered that by containing ~20 layers, each of the disadvantages of the fragrance can be improved and the excellent value of the fragrance T1 can be fully demonstrated. Furthermore, it has been found that the oil-soluble component is very well compatible with this norbornane derivative, and the mixture produces an integrated and elegant aroma as a perfume.

It has been observed from many experiments by the inventors that for this purpose sandalwood old beetroot fl 4'1 (i
41 other than substances (f ingredients of substances cause unwellness, contained in plants of the genus Nucifera of the family Nucifera / 111 M
The content of the sex component for the norbornane derivative is 0.
．． 5 to 20 weight units, particularly preferably 1 to 15 weight units. Regarding this content, 0.
If the amount is less than 5 M', almost no effect is observed, and it is economically disadvantageous, and if the amount is more than 20 by weight, the aroma of the additive will overwhelm the original aroma of the norbornane derivative! Not only will it be difficult to implement the 1 yen tax, but it will also be at a considerable economic disadvantage. The addition operation for containing 0.5 to 20 parts of the oil-soluble component described above can be carried out by any of the following methods.

(a) Norbornane derivatives: Sandalwood F
A one-way system that extracts P and AM fragments by bringing them into direct contact.

(b) Sandalwood publication A blending method in which oil-soluble components obtained by solvent extraction or steam distillation of fragments of sandalwood plants are added to norbornane derivatives.

(c) A blending method in which an oil-soluble component collected from a plant of the genus Sandalwood in the family Nilaceae is purified, an essential oil component or a specific component thereof is separated, and this is added to all norbornane derivatives.

(d) A blending method in which a lenonoid containing lignin as an oil-soluble component collected from a plant of the genus Helicopteraceae and the genus Kugun is added to a norbornane derivative.

(e) A method that uses methods (a) to (d) above in combination, and the order of the methods may be changed.

Further, as can be seen from the structural formula, the norbornane derivatives represented by formulas (I) and (1'l) have R4
positional isomers, endo-echino isomers of each substituent on the norbornane ring, positional isomers of double bonds and optical differences due to the presence of double bonds/su-trans isomers and optical differences due to the presence of asymmetric carbon atoms/1-isomers However, the method of the present invention applies not only to pure products of these isomers such as J'1 but also to commercially available mixtures of isomers obtained by industrial synthesis methods. It can also be conveniently applied to mixtures of fully hydrogenated, incompletely hydrogenated and unhydrogenated double bonds in formulas (1) and (II). It can also be applied without any inconvenience.

As for which of the sandalwood and sandalwood genus 41b is compatible with which norbornane derivative, it is best to combine products that have the same aroma or similar aroma to each other. 1.Although this is the general rule, any combination (104) will have oxidation stability
Improved photostability and thermal stability J'1. Therefore, these combinations can be arbitrarily selected depending on the subsequent formulation of fragrance A' and I and the commercialization.

The strained perfume composition of the present invention may be supplemented with any known natural or synthetic perfume ingredient or perfume diluent, as long as the effect thereof is not impaired.

The stabilized wood-based fragrance composition of the present invention can be used monthly as a flavoring agent for various perfume bases, cosmetics, soaps, daily necessities, etc., as well as flavor components, synthetic essential oil components, deodorant components, and deodorant components. It can be widely used as odorant ingredients and fragrance diluents.

Next, the present invention will be explained in detail with reference to Examples, and as a representative example, the case where the above-mentioned compounds A to G'F are used will be explained.

Example 1 Compound A107 with meat from India] 1, ", j powder (containing 5% oily component) 10! i'f, p was added, kneaded well, and left at room temperature for 3 days. Added methanol and dissolved. After all the components were extracted, methanol was distilled off, and the residue was tested.Compound 1 was used as it was as a comparative example.

The oxidation stability was determined by applying a thin layer to each watch glass of the sample, leaving it in the air, and examining the aroma after 30 hours. After keeping it at room temperature for 2 hours under irradiation with a high-pressure mercury lamp, the aroma was examined, and as for thermal stability, the sample was applied near the odorless line, ignited, and the aroma tone decreased. The results are shown in Table 2 below R1.

Table 2 Example 2 Perform all the same operations as Example 1 using compound B107,
Example 3 Compound ClO2 was mixed with natural sandalwood oil produced in various places.
Comparative Example in which only Compound C was mixed and the oxidation stability was investigated according to the method of Example VIIr'-1. The results are shown in Table 4 below.

Table 4 Example 4 A liquid containing Australian meat seed oil as shown in Table 5 below was placed in a flask equipped with a reflux condenser.
Heated to 0°C and pumped air k at a rate of 500 m6/min.
After infusing for a period of time, changes in color and aroma of the liquid were examined. The results were as shown in Table 5 below.

Table 5: When the content of Australian meat seed oil exceeds 20%, the aroma becomes abnormally strong and no obvious results are observed. Furthermore, the fifth
In the notes column of the table, "high" indicates all the samples with many peaks of decomposed products in gas chromatography analysis, and "small" indicates those with few peaks of decomposed products. In this example, oxidation stability and thermal stability were investigated, and in the table, if the stability is medium to small, it indicates that the quality is improved compared to the comparative example.

Example 5 A rose-based fragrance was prepared using Compound E to which 5% of Mysore-produced nutwood oil fI was added and another with no addition (comparative example) as sandalwood fragrances. Its blend C: β-phenylethyl alcohol 15. Qr, methylionone 15
;(H', Rosinol 30.OS', Cousalide 15
．． 0! i', rose oil 1'5.01i', and the sandalwood fragrance io, o y, a total of 1007. This rose
Two base fragrances were kneaded into soap, molded, and then sliced to make paper soap. Place this paper soap in a well-ventilated room/i
As a result of examining the degree of change in aroma for 2 weeks after lowering the temperature, it was found that the comparative example's aroma changed quickly, while the example's aroma changed to a lesser degree even after 2 weeks. .

Example 6 Compound F with Indonesian meat seed oil (made in Singapore)
A base fragrance for formulation was prepared using sandalwood oil fragrances containing 10% of f: and those containing no additive (comparative example). Is the formulation ethylene pranrate 4.0? ,β
-Phenylethyl alcohol so, or, methylionone 2.49. Bennol salicylate 5.67 and the white 11·°l fragrance 8.01, for a total of 1007. The base fragrance for this formulation has a musky green rose odor. The aroma of the comparison example was found to be "good" in the organoleptic/synthetic test, but the aroma of this example was "excellent", indicating that the aroma was considerably improved by blending 10% sandalwood oil. Ri,ta.

Example 7 Compound G107 was used in the same manner as in Example 1, and a similar comparative test was conducted. The results are shown in Table 6 below.

Patent applicant: Japan Petrochemical Co., Ltd. Agent Hajime Maetaka, patent attorney

Claims (2)

[Claims] (1) At least one norbornane derivative selected from the liver consisting of the compounds represented by the following formulas (I) and (n), is added with an oil-soluble component contained in a plant of the genus Nucifera of the family Nucifera. 〜20＠HA′ Composition 1: Here, in formulas (1) and (II), Ro and R2 are the same or different hydrogen atoms. Atom, number of carbon atoms 1~
Representing 4 aliphatic hydrocarbon residues or phenyl groups,
R3 and R4 are all hydrogen atoms or methyl groups, and R5... is an alkyl group, alkenyl group, or alkylidene group having 2 to 3 carbon atoms, and == is a carbon-carbon bond. indicates that the carbon-carbon bond is a single bond or a double bond. cannot be double bonds at the same time. (2) The stabilized wood-based fragrance composition according to claim 1, wherein the norbornane derivative is a compound represented by the following formula (ffl) or (IV), wherein both formulas ( The definition of the symbols in III) and (IV) is R
The formula (1) except that 1 is a methyl group or an ethyl group
) and (II), respectively.