JP2943038B2 - Rabdanum oil reforming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing labdanum oil having an improved odor, which is useful as a compounded fragrance material.

[0002]

2. Description of the Related Art Labdanum oil is a black, rather viscous liquid obtained from a plant belonging to the genus Cistus. It has a plant-derived amber animal-like aroma and is used in various compounded fragrances. Such Lab Dunham oils include:
In general, crude labdanum oil, which is a resin obtained by boiling a plant containing rabdanum oil in water and separated, treated rabdanum oil obtained by removing inorganic solid components from the crude rabdanum oil, and purified rabdanum oil obtained by distilling or fractionating the treated rabdanum oil Is used.

[0003] However, conventional crude lab dunam oil, treated lab dunam oil and refined lab dunam oil all have a woody off-flavor like a cederwood and a stiffness.
The color was black to black-brown. Therefore, if these Lab Dunham oils are blended with the blended fragrance to give the characteristic amber animal feeling, the odor will not come out due to the woody fragrance that comes off in terms of odor. In view of this, there is a problem that the product is colored when used in soaps, detergents and the like.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present invention is intended to eliminate the woody and smelling sensation of cederwood that is present in conventional crude labdanum oil, treated rabdanum oil and refined labdanum oil. It is an object of the present invention to provide a method for modifying labdanum oil which enhances animal feeling and further reduces both coloring and viscosity.

[0005]

Under these circumstances, the present inventors have conducted intensive studies on the components of rabdanum oil, and as a result, heat-treated the carboxylic acid, phenols and other acids contained in the rabdanum oil under normal pressure to produce the animal. A feeling that increases the perfume material without woody odor,
If the resulting heat-treated product is purified by distillation under specific conditions,
The present inventors have found that decolorization, lowering of viscosity and concentration of odor components are possible, and that they can be widely used for compounded fragrances, and thus completed the present invention.

That is, the present invention provides a modified ravdanum oil characterized in that a raw rabdanum oil having a woody off-flavor is treated in the order of the following steps A, B and C to remove the off-flavor. It provides a quality method. Step A: A step of extracting an acidic component of Rabdanum oil as a salt by adding and mixing an aqueous alkali solution to the raw Rabdanum oil and then separating the aqueous layer. Step B: Adding an acidic substance to the aqueous layer separated in Step A For separating and obtaining the acidic component of the released Rabdanum oil Step C: a step of heat-treating the acidic component of Rabdanum oil obtained in Step B at 200 to 350 ° C. for 0.1 to 10 hours

If the acidic component of the heat-treated Rabdanum oil obtained in the step C is distilled and refined as the step D following the step C, the decolorization of the product, the reduction of the viscosity and the concentration of the odorous component are also achieved. It is possible and preferred.

The raw rabdanum oil used in the present invention is not particularly limited, and any oil can be used. (A) A crude resin, which is a resin obtained by boiling a plant containing rabdanum oil in water and separating it. Rabdanum oil, (b) treated rabdanum oil obtained by removing inorganic solid components of the crude rabdanum oil, and (c) refined rabdanum oil obtained by distilling or fractionating the treated rabdanum oil are preferable. . These can be used alone or in combination of two or more.

[0009] Such crude Labdanum oil is a Cistus species Cist
This resin is obtained by boiling us Ladaniferus L. in water, generally in alkaline water, and a commercially available product can also be used. The treated labdanum oil is obtained by dissolving the crude labdanum oil in a solvent such as ethanol and removing insoluble inorganic solid components, but a commercially available product can also be used. The refined lab dunnam oil is obtained by distilling or fractionating the treated lab dunnam oil under the conditions of, for example, a tank temperature of 140 to 240 ° C. and a degree of vacuum of 2 Torr. Each of these Labdanum oils has a woody off-flavor like a Cedarwood.

Hereinafter, each step will be described in detail.

Step A: This step is a step of extracting an acidic component of the raw Rabdanum oil with an alkali, and is carried out by a normal alkali neutralization reaction, for example, by adding an aqueous alkali solution to the raw Rabdanum oil and mixing and stirring. Will be The alkali used here is not particularly limited as long as it is capable of neutralizing carboxylic acids, phenols, and the like, which are acidic components of Rabdanum oil, and forming a water-soluble neutralized salt. Alkali metal hydroxide,
Alkaline earth metal hydroxides, alkali metal carbonates and alkali metal bicarbonates are preferred, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are particularly preferred. The use amount of these alkalis is preferably 0.5 to 10 times equivalent, particularly preferably 1.0 to 5.0 times equivalent of the acid equivalent of the raw rabdanum oil. The conditions of the mixing and stirring are not particularly limited,
Preferably in the presence of an organic solvent, 0 ~ 150 ℃, especially 50 ~ 100
It is preferably carried out at 0.1 ° C. for 0.1 to 5 hours, especially 0.5 to 2 hours. The organic solvent that can be used is not particularly limited as long as it is stable under alkaline conditions, and examples thereof include hexane, heptane, cyclohexane, benzene, toluene, xylene and the like, and mixtures thereof. Alkaline extraction of the raw rabdanum oil is performed by mixing and stirring, separating the reaction mixture by a usual method, removing the oil layer, and collecting the aqueous layer.

Step B: This step is a step in which the salt of the acidic component of Rabdanum oil obtained by the alkali extraction in Step A is metabolized with an acid and recovered. This operation is carried out by adding an acid to an aqueous alkali solution of a salt of an acidic component, mixing and stirring to make it acidic, and separating and obtaining an acidic component of the released Rabdanum oil. The acid used here is not particularly limited as long as it is capable of double-decomposing a salt with an alkali metal such as carboxylic acid and phenols, which is an acidic component of Rabdanum oil, and releasing carboxylic acids and phenols. Sulfuric acid, hydrochloric acid, phosphoric acid and the like are preferred from an economic viewpoint. The amount of these acids used is 1.0 to 5 of the alkali used.
Double equivalents, especially 1.2 to 3 equivalents are preferred. The conditions of the mixing and stirring are not particularly limited, but are preferably in the presence of an organic solvent and generate heat due to neutralization.
At 0.1 to 5 hours, especially 0.3 to 1 hour at 0 to 100 ° C, especially 50 to 80 ° C, 0.1 to 5 hours.
It is preferred to stir for ~ 5 hours, especially 0.5-2 hours. The organic solvent that can be used is not particularly limited as long as it is stable under alkaline and acidic conditions, and examples thereof include hexane, heptane, cyclohexane, benzene, toluene, xylene and the like, and mixtures thereof. To remove excess acid after acid re-extraction, after the above mixing and stirring, the reaction mixture is separated by an ordinary method to remove an aqueous layer, and then the oil layer is washed with water and distilled by an ordinary method as necessary. do it.

Step C: This step is a step of heat-treating the acidic component of Rabdanum oil obtained in Step B. The heat treatment is performed at 200 to 350 ° C., preferably at 250 to 300 ° C., for 0.1 hour.
It is carried out by heating for 1 to 10 hours, preferably 0.5 to 2 hours, and is preferably carried out under a nitrogen atmosphere while stirring under normal pressure to avoid generation of odor and coloring due to oxidation.

The acidic component of the thus-obtained rabdanum oil has no animal-like odor like a Cedarwood-like and flaky woody odor, but has an enhanced animal-like odor. For the purpose of concentrating the components, it is preferable to carry out distillation purification by the following step D.

Step D: In this step, the acidic component of the labdanum oil heat-treated in Step C is purified by distillation to remove the color, reduce the viscosity, and concentrate the odor component.
In this distillation purification operation, if a hydrocarbon is added to the heat-treated Rabdanum oil acidic component obtained in the step C and then distillation is performed, a fraction can be efficiently obtained, which is preferable. As a hydrocarbon that can be used, the boiling point at 760 mmHg is 260 to 400
C., preferably 300 to 350.degree. C., or a saturated hydrocarbon or a mixture thereof, more preferably liquid paraffin.
Distillation conditions are 1-3 mmHg, the maximum temperature in the tank is 220-2
Preferably it is 50 ° C.

When the modified rabdanum oil obtained as described above is blended in a fragrance composition, the blending amount is 0.1%.
1 to 40% by weight, especially 0.5 to 15% by weight is preferred.

Further, in the fragrance composition, components such as diethyl phthalate, dipropylene glycol, ethyl diglycol, hercoline D (methyl dihydroabietic acid) and natural fragrances such as sandalwood oil and patchouli oil are further contained. Can be blended.

Such a fragrance composition can be obtained by mixing and agitating the above components with the modified Rabdanum oil according to the method of the present invention.

[0019]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 500 cc 4 with a stirrer, thermometer and Dimroth
200 g of Rabdanum resinoid (manufactured by BIO), which is treated Rabdanum oil, was added to a one-necked flask, and 200 g of a 10% aqueous sodium hydroxide solution and 400 g of toluene were added, followed by stirring at 90 ° C. for 30 minutes in a nitrogen gas atmosphere. The toluene layer was removed by standing liquid separation, 400 g of toluene was further added to the aqueous layer, and the mixture was stirred similarly and left to stand for liquid separation to remove the toluene layer.
400 g of toluene was added to the obtained aqueous layer, and the mixture was stirred, and 25 g of concentrated sulfuric acid was slowly dropped while paying attention to the temperature in the tank.
After the dropwise addition, the temperature was raised to 90 ° C. in a nitrogen gas atmosphere, and the mixture was allowed to stand still to remove an aqueous layer. 10% Glauber's salt solution was added to the obtained oil layer, and the mixture was stirred and allowed to stand still. The toluene was distilled off from the oil layer.
As a residue, 71 g of Rabdanum oil acid part was obtained. 50 g of the obtained acidic part was heated and stirred at 260 ° C. for 30 minutes in a nitrogen gas atmosphere. The obtained Rabdanum heat-treated oil had an amber animal scent with an emphasis on animal scent, excluding a cedarwood-like and fragile smell compared to before the treatment. Thereafter, the temperature in the tank was cooled to 100 ° C., and liquid paraffin # 60s (manufactured by Chuo Kasei Co., Ltd., bp 278-4)
(22 ° C.), 50 g was dropped, and first distillation under reduced pressure (減 圧 150 ° C./2)
Torr), the temperature is further increased, and the distillation fraction (185) is removed.
~ 240 ° C / 2 Torr). This product had significantly reduced coloring and viscosity. The distillation fraction obtained here was used as modified Labdanham oil in the following Reference Example 1
Used in

Reference Example 1 A fragrance composition having the formulation shown in Table 1 was prepared.

[0022]

[Table 1]

Compared with the comparative product, the product of the present invention was a leather-like fragrance composition in which an animal feeling was emphasized.

[0024]

According to the method of the present invention, a woody off-flavor which is cedarwood-like and rustling is removed, an amber animal-like fragrance with an enhanced animal fragrance, and coloring is greatly reduced. A high quality labdanum oil is obtained, which can be widely used as a compounding flavoring material such as soap and detergent.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Nao Toi 6-21-2 Nakashitsu, Sakura City, Chiba Prefecture (72) Yoshiaki Fujikura 271-6, Yamamotocho, Utsunomiya City, Tochigi Prefecture (56) References Patent 89272 (JP) , C2) (58) Fields investigated (Int. Cl. ⁶ , DB name) C11B 9/02 C11B 3/04 C11B 3/06 CA (STN)

Claims (8)

(57) [Claims] 1. A method for reforming rabdanum oil, comprising treating a raw rabdanum oil having a woody off-flavor such as Cedarwood in the order of the following steps A, B and C to remove the off-flavor. Step A: A step of extracting an acidic component of Rabdanum oil as a salt by adding and mixing an aqueous alkali solution to the raw Rabdanum oil and then separating the aqueous layer. Step B: Adding an acidic substance to the aqueous layer separated in Step A For separating and obtaining the acidic component of the released Rabdanum oil Step C: a step of heat-treating the acidic component of Rabdanum oil obtained in Step B at 200 to 350 ° C. for 0.1 to 10 hours 2. A raw rabdanum oil having a woody off-flavor like a Cedarwood, comprising: (a) a crude labdanum oil which is a resin obtained by boiling a plant containing rabdanum oil in water and separating the same;
(B) selected from the group consisting of treated rabdanum oil obtained by removing an inorganic solid component of the crude labdanum oil, and (c) refined labdanum oil obtained by distilling or fractionating the treated rabdanum oil. The method for reforming Rabdanum oil according to claim 1, wherein one or more kinds are used. 3. The alkali used in the step A is one or more selected from the group consisting of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate and an alkali metal bicarbonate. The method for reforming Rabdanum oil according to claim 1 or 2. 4. The method for reforming rabdanum oil according to claim 1, wherein the acidic substance used in the step B is one or more selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid. . 5. The method according to claim 1, wherein the heat treatment in the step C is performed in a nitrogen atmosphere. 6. The method for reforming rabdanum oil according to any one of claims 1 to 5, further comprising the following step D after step C. Step D: Step of distilling and refining the acidic component of the labdanum oil heat-treated in Step C 7. The distillation purification in step D, wherein the boiling point is 260 to 4
After the addition of the hydrocarbon compound at 00 ° C./1 atm.
The method for reforming Rabdanum oil according to claim 6, which is performed by collecting a fraction up to 1 ° C / mmHg. 8. The method according to claim 7, wherein the hydrocarbon compound is liquid paraffin.