JPH0150360B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention removes the causative substance from a natural perfume oil containing bergapten, which causes harmful effects on the skin (phototoxicity), without adversely affecting the aroma, color, component balance, yield, etc. of the natural essential oil.
The present invention relates to a manufacturing method that can industrially advantageously produce high-quality, non-phototoxic natural essential oils. Natural essential oils are used in perfumes, colognes, creams,
It is widely used as a fragrance for cosmetics such as lotions, lipsticks, white powders, foundations, pomades, ticks, and hair creams. However, it is well known that bergapten, which is contained in natural essential oils such as bergamot oil, lime oil, lemon oil, orange oil, and grapefruit oil, has phototoxicity. Conventionally, the method for removing compounds with coumarin cores such as bergapten is to obtain a distillate essential oil by distilling natural essential oil, bergamot oil, under reduced pressure at a temperature that does not change the components of bergamot oil. It is hydrolyzed with an alcoholic alkali to remove furocoumarins by converting them into an alkali salt form of the hydrolyzate, and the remaining neutral oil is combined with the distilled essential oil, which irritates the skin. Proposal to produce bergamotu essential oil (Tokukosho)
35-15363) has been made. However, in this method, the useful neutral oil components other than bergapten tend to undergo side reactions (oxidation, polymerization, isomerization, decomposition, etc.) due to the alkali during hydrolysis, and the aroma of natural perfume oil , deterioration of color tone, component balance, etc., coloration, aroma change, etc.
It has been pointed out that there are many technical defects (Japanese Unexamined Patent Publication No. 55-3434, Paragraph 2, left column). As another method, lemon oil is distilled under reduced pressure at a temperature that does not change the components of lemon oil to obtain a distillate essential oil, and the distillation residue is cooled in the presence of a nonpolar solvent to obtain a distilled essential oil. crystallizes psoralen compounds,
A method for producing a natural essential oil that does not contain psoralen compounds has been proposed, which is characterized by combining the essential oil obtained by removing the nonpolar solvent from the residual liquid with the above-mentioned distilled essential oil (Japanese Patent Application Laid-Open No. 55−3434). However, it is difficult to sufficiently remove bergapten with this method (extraction from distillation residue), and this fact is clear from the fact that JP-A-56-70096 was proposed as an improved invention. be. As a result of intensive research to develop a method for producing non-phototoxic natural essential oil from natural essential oil containing bergapten, the present inventors found that when the distillation residue of natural essential oil containing bergapten is reduced as described below. In this method, bergapten is converted into a non-phototoxic compound, and the component extracted with an organic solvent from the reduction treatment mixture (the distillation residue obtained in the third stage described below) is combined with the distillate essential oil obtained in the first stage described later. The present invention has been completed based on the discovery that by doing so, it is possible to obtain natural essential oils of excellent quality and without phototoxicity without adversely affecting the aroma, color tone, component balance, yield, etc. of natural essential oils. Therefore, an object of the present invention is to provide a method for industrially and easily producing a high-quality natural essential oil that does not substantially contain bergapten and has no phototoxicity from a natural essential oil containing bergapten. Many other objects and advantages of the invention will become more apparent from the description below. The present invention comprises: (1) a first step of distilling a natural essential oil containing bergapten under reduced pressure conditions to collect a distilled essential oil that does not substantially contain bergapten; and (2) converting the distillation residue into a saturated fat. (3) Adding an organic solvent to the resulting mixture after the reduction treatment and extracting it, washing the obtained extract with water and dehydrating it; (4) A fourth step in which the distilled residue after distilling off the organic solvent is mixed with the distilled essential oil collected in the first step.
A method for producing a natural essential oil without phototoxicity, characterized by comprising the steps of: Hereinafter, embodiments of the present invention will be explained in detail. Examples of natural essential oils containing bergapten that can be used in the method of the present invention include bergamot oil, lemon oil, orange oil, lime oil, grapefruit oil, mandarin oil, and petitculene oil. In the first step, the natural essential oil containing bergapten is distilled under reduced pressure conditions by appropriately selecting the degree of reduced pressure and temperature so as to obtain a natural essential oil that does not substantially contain bergapten without altering the natural essential oil. can be done. Generally, conditions can be adopted that do not impair the aroma of the essential oil components contained in the natural essential oil, such as a temperature of 125° C. or less and a degree of vacuum of about 10 mmHg or less. Generally, it is preferable to select a lower temperature and reduced pressure. Further, the amount of distillation obtained by distillation is selected depending on the content of bergapten in the natural essential oil, but generally a distillation amount of about 95% by weight based on the raw natural essential oil is adopted. It is best to distill as much as possible without sacrificing the aroma. As described above, the distilled essential oil obtained by vacuum distillation in the first stage is mixed with the distillation residue obtained in the third stage, but is stored until then. The distillation residue obtained in the first stage is a saturated aliphatic lower 1
After dissolving in a alcohol (solvent), sodium borohydride or sodium borohydride as a reducing agent and nickel boride are added to the solution for reduction treatment. (Second stage). By this reduction treatment, bergapten, which is contained in a relatively large amount (approximately 3 to 6% by weight) in the distillation residue of the first stage, can be converted into a non-phototoxic compound. Examples of the saturated aliphatic lower monohydric alcohol that dissolves the distillation residue include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, n-amyl alcohol, and isoamyl alcohol. be able to. The amount of the lower monohydric alcohol used is preferably in the range of 5 to 10 times the weight of the distillation residue. In the reduction treatment, sodium hydride alone or nickel boride as a reducing agent is added to the alcohol solution of the distillation residue at a rate of usually 0.1% by weight based on the weight of the distillation residue.
This is carried out by adding ~0.2 times the weight and stirring for approximately 5 to 7 hours at a temperature ranging from 40°C to the reflux temperature of the alcohol. Bergapten is not substantially present in the resultant mixture after reduction treatment, and for example, even when analyzed by high-speed chromatography, no bergapten peak is observed. In the present invention, the distillation residue of the first stage may be subjected to reduction treatment in this way, but if necessary, as another method (addition step), the distillation residue of the first stage is dissolved in a non-polar solvent, , the solution is cooled, the precipitated solids are separated and removed (separately), and the remaining liquid (
The distillation residue after distilling off the nonpolar solvent may be dissolved in the lower alcohol and subjected to reduction treatment as described above. Implementation of this additional step increases the number of steps, but has the advantage that the time required for the reduction treatment is shortened because the content of bergapten in the distillation residue is reduced. Incidentally, examples of non-polar solvents that can be used in this addition step include petroleum benzene, petroleum benzene, n
-hexane, n-pentane, isopentane, n-octane, cyclohexane and the like. The amount used is 1 to 1 based on the weight of the distillation residue in the above step.
Five times the weight is preferred. Further, the temperature at which the nonpolar solvent solution of the distillation residue in the first stage is cooled is preferably 10°C or lower, preferably 0°C or lower. In addition, vacuum distillation is preferably used as the distillation for distilling off the nonpolar solvent from the residual liquid after separating and removing the precipitated solid matter. The product mixture after reduction treatment in the second stage is distilled to remove the saturated aliphatic lower monohydric alcohol contained therein, then a hydrophobic solvent is added to the residue for extraction, and the extract is washed with water. After dehydration, the extract is distilled to remove the hydrophobic solvent contained therein (third step). In this third step, distillation for distilling off (recovering) the saturated aliphatic lower monohydric alcohol and the hydrophobic solvent from each of the solutions is preferably vacuum distillation. As the hydrophobic solvent (extraction solvent) added to the residue after distilling off the saturated aliphatic lower monohydric alcohol, for example, ethyl ether, methyl ethyl ether, benzene, chloroform, methylene chloride, etc. are preferable. Extraction with the hydrophobic solvent can be sufficiently carried out by conventional extraction operations. Washing this extract with water is
This is done to separate and remove the remaining reducing agent dissolved in the extract, and it is important to wash thoroughly with water until the pH of the extract layer becomes neutral. Since the washed extract contains a small amount of water, it is desirable to add an appropriate amount of an inert dehydrating agent such as anhydrous sodium sulfate to sufficiently dehydrate it. The hydrophobic solvent extract after dehydration is distilled to remove the hydrophobic solvent, and this distillation is also preferably distilled under reduced pressure. The distillation residue (pale yellow extract) after removing the hydrophobic solvent by this distillation is added to the distilled essential oil collected in the first step and mixed (combined) to form a product. (Fourth stage) The purified natural essential oil obtained in this way is substantially colorless and transparent, has no foreign odor, retains the aroma of the natural essential oil without loss, and is rich in so-called naturality. It has a scent. Moreover, it does not irritate the skin and has no phototoxicity. Furthermore, it does not contain not only bergapten, which is known as a phototoxic component, but also oxyboisedanin and the above-mentioned psoralens.
For example, even in high performance liquid chromatography analysis, no peaks of these phototoxic components are observed. According to the method of the present invention, the aroma of the natural essential oil,
It is possible to obtain high-quality natural essential oils with high utility value without adversely affecting color tone and component balance (useful essential oil components), without phototoxicity, with good reproducibility, and with specificity of its action and effect. Significant. Example 1 1.0 kg of bergamot oil containing 1.8% (weight) of bergapten was distilled under reduced pressure at 70°C/2 mmHg.
Colorless oil (distillate essential oil) as distillate oil up to 0.96
Got Kg. As a result of high performance liquid chromatography analysis of this colorless oil, no peak of bergapten was observed. Next, 277 g of methyl alcohol was added as a solvent to 40 g of this distillation residue, and after dissolving it,
Add 4.0% sodium borohydride to this solution under stirring.
g was gradually added over 1 hour. Thereafter, the mixture was heated under reflux for 4 hours. After such reduction treatment, the resulting mixture was distilled under reduced pressure to remove methyl alcohol. As a result of high performance liquid chromatography analysis of this distillation residue, no peak of bergapten was observed. Next, add 300ml of ethyl ether to 32g of this distillation residue.
of the ethyl ether layer of the extract.
The extract was washed with water until the pH became neutral, and then anhydrous sodium sulfate was added to the extract to dehydrate it, and ethyl ether was distilled off. 20.0 g of the distillation residue (pale yellow oil) thus obtained was added to the distilled essential oil obtained earlier and mixed with stirring to obtain purified bergamot oil 980 g.
I got g. As a result of high performance liquid chromatography analysis of this purified bergamot oil, bergapten, oxyboisedanine and psoralen (psoralen, 4-methylpsoralen, 4,4'-dimethylpsoralen,
The peaks of 4,5'-dimethylpsoralen, 4',8-dimethylpsoralen, 4,5',8-trimethylpsoralen, 8-methoxypsoralen, and 5-methoxypsoralen were not observed. In addition, this refined bergamot oil and the commercially available bergamot oil (bergapten-containing bergamot oil)
A sensory test was repeated 10 times by 10 expert inspectors regarding the smell of . As a result, 9 out of 10 people confirmed that there was no difference in aroma between the two samples. Further, as a result of conducting a phototoxicity test as described below, this purified bergamot oil was confirmed to have no phototoxicity. Phototoxicity test method The back of a white rabbit weighing 2.5 to 3 kg was shaved.
After 24 hours, add ethanol diluted solution of sample to 2 x 2 ^cm2.
Apply 50μ in two rows. One row was covered with aluminum foil and exposed to UV-A after 1 hour.
(320 nm to 400 nm) was irradiated for 1 hour. The light source used was 10 Toshiba BLB lamps equipped with a glass filter. The amount of energy at this time is 30×
It was 107ergs/ ^cm2 . Judgments were made according to the following ratings for erythema and edema immediately after irradiation, 24 hours later, and 48 hours later. Rating: No macroscopic change 0 Mild or sparse erythema 1 Moderate erythema 2 Severe erythema and edema 3 Comparing the response between the UV-A irradiated area and the non-irradiated area, the irradiated area showed a strong reaction The case was judged as phototoxicity (+). The average reaction intensity was calculated as follows. Average reaction intensity = total score of each rabbit / number of rabbits used in the experiment Test results: In the table, the numbers in parentheses in the UV (-) and UV (+) sections indicate the average intensity. The number in the denominator represents the number of domestic rabbits used in the experiment, and the number in the numerator represents the number of domestic rabbits that responded to the stimulus.

[Table] As a result, commercially available bergamot oil has a significant phototoxic effect, but no phototoxicity was detected in the purified bergamot oil according to Example 1 of the present invention. Example 2 The bergamot oil of Example 1 was similarly distilled under reduced pressure to obtain 0.96 kg of distillate oil (distilled essential oil of colorless oil) up to 70°C/mmHg and 40.0 g of distillation residue. Add 316 g of methyl alcohol to 40 g of this distillation residue,
Add 40 g of nickel boride obtained in advance from nickel chloride and sodium borohydride, and then add 4.5 g of sodium borohydride little by little over 1 hour while stirring at 40°C to 50°C. After the addition, the mixture was heated under reflux for 4 hours. Thereafter, methyl alcohol was distilled off under reduced pressure, and 30 g of the residue was extracted with 300 ml of chloroform. After adding water to this extract and washing with water until the pH of the chloroform layer becomes neutral, anhydrous sodium sulfate is added to dehydrate the extract, and chloroform is distilled off under reduced pressure. Resulting residue (pale yellow oil)
25 g was thoroughly mixed with 0.96 kg of distilled essential oil obtained earlier to obtain 985 g of refined bergamot oil. As a result of carrying out the same procedure as in Example 1, it was confirmed that this purified bergamot oil did not contain bergapten, oxypoisedanine, and psoralen. Furthermore, no phototoxicity was detected as shown in Table 2. Furthermore, the results of the sensory test regarding odor are as follows:
10 out of 10 people confirmed that there was no difference in aroma compared to commercially available bergamotu oil (untreated, containing bergapten).

[Table] Example 3 Purified bergamot oil was produced in the same manner as in Example 1, except that each alcohol shown in Table 3 below was used instead of methyl alcohol. Yield of each refined bergamot oil obtained, yield,
The results of phototoxicity and aroma are shown in Table 3. In addition, the distilled essential oil of bergamotsu oil is 960g each.
It was hot. Also, "good aroma" means that no difference was observed in the aroma compared with the commercially available bergamot oil used.

[Table] From the above results, it was confirmed that saturated aliphatic lower monohydric alcohol is preferable as the solvent for the distillation residue in the reduction treatment. Example 4 1.0 kg of bergamot oil containing 0.3% by weight of bergapten was distilled under reduced pressure to obtain 0.96 kg of distillate essential oil (colorless oil) at a temperature of up to 70° C./2 mmHg. Next, add 400 ml of petroleum ether to 40 g of this distillation residue.
and cooled to 0°C. The precipitated crystals and insoluble matter are separated, and the petroleum ether is distilled off under reduced pressure. 237 g of methyl alcohol was added as a solvent to the residue after petroleum ether was distilled off, and 2.4 g of sodium borohydride was added little by little over 1 hour to 40 to 50 g of methyl alcohol.
℃ and add with stirring. After the addition, the mixture was heated under reflux for 4 hours. Thereafter, the resulting mixture was distilled under reduced pressure to remove methyl alcohol. Next, the residue is extracted with 300 ml of ethyl ether, washed with water until the pH of the ethyl ether layer becomes neutral, dried over anhydrous sodium sulfate, and then ethyl ether is distilled off. After distilling off the ethyl ether, 19 g of the residue (slightly yellow oil) was extracted from the previously obtained distilled essential oil.
The mixture was added to 960 g and mixed with stirring to obtain 979 g of purified bergamot oil. This purified bergamot oil was examined in the same manner as in Example 1, and it was confirmed that it did not contain bergapten, oxypoisedanine, and psoralen. Also, no phototoxicity was detected. In addition, as a result of a sensory test regarding odor, 10 out of 10 people confirmed that there was no difference in aroma compared to the commercially available bergamot oil. Example 5 Lime oil containing 0.25% by weight of bergapten
1.0 kg was distilled under reduced pressure to obtain 960 g of distilled essential oil (colorless oil) as distilled oil up to 70°C/2 mmHg.
Next, 300 ml of petroleum ether was added to 40 g of this distillation residue, and the mixture was cooled to 0°C. The precipitated crystals and insoluble matter are separated, and the petroleum ether is distilled off under reduced pressure. After distilling off the petroleum ether, 237 g of ethyl alcohol was added as a solvent, and 2.4 g of sodium borohydride was added little by little over 1 hour at 40°C to 50°C.
℃ and add with stirring. After addition, heat to reflux for 4 hours. After that, ethyl alcohol was distilled off under reduced pressure,
20 g of the residue is extracted with 300 ml of benzene, washed with water until the pH of the benzene layer becomes neutral, dried over anhydrous sodium sulfate, and then the benzene is distilled off under reduced pressure. Next, this residue (pale yellow oil) (15 g) was added to 960 g of the previously obtained distilled essential oil and mixed with stirring to obtain 975 g of refined lime oil. This refined lime oil was examined in the same manner as in Example 1, and it was confirmed that it did not contain bergapten or psoralen. Also, no phototoxicity was detected. In addition, the results of a sensory test regarding smell,
9 out of 10 people confirmed that there was no difference in aroma compared to the lime oil they used (untreated). Example 6 1.0 kg of lime oil containing 0.25% by weight of bergapten was distilled to obtain 960 g of distilled essential oil at a temperature of up to 70°C/2 mmHg. Next, 237 g of ethyl alcohol and 4.0 g of nickel boride were added to 40 g of the distillation residue, and 2.4 g of sodium borohydride was added little by little over 1 hour.
The addition was followed by refluxing for 4 hours with stirring at ~50°C.
Thereafter, ethyl alcohol was distilled off under reduced pressure. Next, 31 g of the residue was extracted with 300 ml of benzene, and the extract was washed with water until its pH became neutral, then dehydrated with anhydrous sodium sulfate, and the benzene was distilled off under reduced pressure.
20 g of distillation residue (pale yellow oil) was obtained. 20 g of this distillation residue was added to 960 g of the previously obtained distilled essential oil and mixed well to obtain 980 g of refined lime oil. As a result of examining this refined lime oil in the same manner as in Example 1, it was found that it did not contain bergapten and psoralen, and that it did not have phototoxicity.
It was confirmed. It was also confirmed that there was no difference in aroma compared to the lime oil used. Example 7 Orange oil containing 0.04% by weight of bergapten
1.0Kg is distilled under reduced pressure to 70℃/2mmHg to produce a colorless and transparent distillate essential oil (orange oil).
Obtained 970g. Add petroleum ether to 30g of this distillation residue.
Add 300ml and cool to 0°C. The precipitated crystals and insoluble matter are separated, and the petroleum ether is distilled off under reduced pressure. 270 g of methyl alcohol is added to the residue after distilling off the petroleum ether, and 20 g of sodium borohydride is added little by little over 1 hour at a temperature of 40 DEG C. to 50 DEG C. with stirring. After addition, heat to reflux for 4 hours. Thereafter, methyl alcohol was distilled off under reduced pressure, and 25 g of the residue was extracted with 300 ml of ethyl ether and washed with water until the ethyl ether layer became neutral. This extract was dehydrated over anhydrous sodium sulfate, and the ethyl ether contained therein was distilled off under reduced pressure to obtain 20 g of a distillation residue (reddish brown oil). This distillation residue
20g was added to 970g of the distilled essential oil obtained earlier and mixed well to obtain 995g of refined orange oil. As a result of high performance liquid chromatography analysis of this purified orange oil, neither a bergapten peak nor a psoralen peak was observed. Further, as a result of conducting a phototoxicity test in the same manner as in Example 1, no phototoxicity was detected. Also, the smell is
Out of 10 professional inspectors compared to used orange oil
10 people confirmed that there was no difference in aroma. Example 8 Lemon oil 1.0 containing 0.2% by weight of bergapten
Kg was distilled under reduced pressure to obtain 965 g of a colorless oil as a distilled essential oil up to 70°C/2 mmHg. Next, distillation residue 35
Add 277g of ethyl alcohol to g as a solvent,
Furthermore, add 20 g of sodium borohydride little by little.
Add with stirring to below 40°C to 50°C for an hour. Thereafter, the mixture is further heated under reflux for 4 hours. After that, ethyl alcohol was distilled off, and 30 g of the residue was dissolved in 300 g of benzene.
Extract in ml. Next, the extract is washed with water until it becomes neutral, then dehydrated with anhydrous sodium sulfate, and the extract is distilled under reduced pressure to remove benzene. 25 g of the pale reddish brown oily substance obtained from the distillation residue was added to 965 g of the distilled essential oil obtained earlier.
g and mixed well to obtain 980 g of purified lemon oil. As a result of high-speed chromatography analysis of this purified lemon oil, no peaks of bergapten, oxypoisedanine, or psoralen were observed. Further, as a result of conducting a phototoxicity test in the same manner as in Example 1, no phototoxicity was detected. In addition, 10 out of 10 expert inspectors confirmed that there was no difference in aroma compared to the lemon oil used. Example 9 1.0 kg of the same lemon oil as in Example 8 was distilled under reduced pressure,
Colorless oil as distillate essential oil up to 70℃/2mmHg
Obtained 965g. Next, 277 g of methyl alcohol is added to 35 g of the distillation residue. Next, 3.5 g of nickel boride prepared from nickel chloride and sodium borohydride was added to this solution, and then 2.0 g of sodium borohydride was added little by little over 1 hour at 40°C.
Add while stirring at 50°C. After addition, heat to reflux for 4 hours. Thereafter, methyl alcohol was distilled off from the resulting mixture under reduced pressure, and 31 g of the residue was evaporated into ethyl ether.
Extract with 300ml and remove the extract (ethyl ether layer).
After washing with water until the pH becomes neutral, dehydrate with anhydrous sodium sulfate. After distilling off the ethyl ether under reduced pressure, 25.0 g of the pale reddish brown oil obtained as the distillation residue was thoroughly mixed with 965 g of the distilled essential oil obtained earlier, and refined lemon oil was added.
Obtained 990g. This refined lemon oil was examined in the same manner as the refined lemon oil obtained in Example 8, and as a result, bergapten,
It has been confirmed that it does not contain oxypoisedanine or psoralen, and is not phototoxic. Additionally, it has been confirmed that there is no difference in aroma compared to the lemon oil used.

Claims (1)

[Scope of Claims] 1 (1) A first step of distilling a natural essential oil containing bergapten under reduced pressure conditions to collect a distilled essential oil that does not substantially contain bergapten; (2) distillation residue; a second step of dissolving in a saturated aliphatic lower monohydric alcohol and performing a reduction treatment in the presence of sodium borohydride or in the coexistence of sodium borohydride and nickel boride; (3) after the reduction treatment; a third step of distilling off the saturated aliphatic lower monohydric alcohol from the resulting mixture, then extracting the residue with a hydrophobic solvent, washing the extract with water, dehydrating it, and then distilling off the hydrophobic solvent; (4) A method for producing a natural essential oil without phototoxicity, comprising a fourth step of mixing the distillation residue after distilling off the hydrophobic solvent with the distilled essential oil collected in the first step. 2 Between the first and second stages, a non-polar solvent is added to the distillation residue obtained in the first stage and cooled to separate and remove the precipitated solids, and then the remaining liquid is distilled to form a non-polar solvent. 2. The manufacturing method according to claim 1, which comprises the step of distilling off the organic solvent and collecting the distillation residue.