JPS6361946B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an octanoic acid lactone represented by the following general formula (hereinafter referred to as the compound of the present invention) and a fragrance composition characterized by containing the compound of the present invention.

[Formula] However, R is an alkyl group having one or two straight chain double bonds having 4 carbon atoms and having a methyl group at the γ-position. The compound of the present invention is a new substance that has not been described in any literature,
This compound was first synthesized by the present inventors and refers to the following compound. 7-Methyl-4-hydroxy-5,7-octadienoic acid lactone (R: _CH2 =C( _CH3 )-CH=
CH-, hereinafter referred to as compound) 7-methyl-4-hydroxy-7-octenoic acid lactone (R: _CH2 =C( _CH3 ) _-CH2 - _CH2- ,
(hereinafter referred to as compound) 7-methyl-4-hydroxy-6-octenoic acid lactone (R: CH3 _- C( _CH3 )=CH- _CH2- ,
(hereinafter referred to as compound) 7-methyl-4-hydroxy-5-octenoic acid lactone (R: _CH3 -CH( _CH3 )-CH=CH-,
Among the compounds of the present invention, the compound is extracted and isolated by the present inventors from quince fruit, and is a compound whose structure has been clarified for the first time, 2,7-dimethyl-4-hydroxy-5,7 - It is a related compound of octadienoic acid lactone, and the compound ~ is synthesized by the synthesis process of the compound and derived from the compound. All of the compounds of the present invention have a unique flavor by themselves, and are useful as flavor raw materials. In other words, the compound exhibits a very ripe, sweet flavor of fruit pulp such as apple or peach, and the compound exhibits a milk-like flavor with a fermented odor element, such as a cheese-like flavor. The compound exhibits a sweet flavor with a buttery flavor, and the compound exhibits a buttery flavor with a fermented milk aroma. As mentioned above, the compounds of the present invention have a unique flavor by themselves, but when one or more of the compounds of the present invention are added to a known flavor composition, the flavor composition has the unique flavor of each compound. While producing aroma characteristics, the fragrance composition harmonizes very effectively with its own fragrance, and especially when two or more compounds are added in combination, the synergistic action of these compounds produces a more than expected effect, making it possible to create a variety of fragrance compositions. It shows excellent effects on improving, modulating and enhancing the aroma of. Next, a specific example will be explained. When added to and used in a fruit-based fragrance composition, it gives a strong natural feel and a strong ripe feeling.
When added to and used in a vanilla flavoring composition, the natural feel will be doubled, and the flavor and strength will stand out. When added to and used in milk or butter-based flavoring compositions, it suppresses the stickiness of milk fat, increases the softness of the flavor, and improves the texture.
Also, when added to tobacco flavoring compositions, when smoking,
Increases the amount of smoke, giving the overall sweetness and softness. On the other hand, when the compound of the present invention is added not only to food-based fragrance compositions but also to cosmetic-based fragrance compositions, it doubles the strength, freshness, and softness as well as naturalness. In particular, this tendency has a dramatic effect on rose and violet fragrance compositions. The addition and blending ratio of the compounds of the present invention to various fragrance compositions can be changed depending on the type of fragrance composition to be added, either singly or in combination of two or more types. Its range is 0.001%~10
% is desirable, but is not limited to this range. Table 1 shows the physicochemical and spectroscopic data of the compound, and describes its synthesis method as a production example. Table 1 (Compound) Apparent properties Colorless and transparent liquid Boiling point 129-132℃/9mmHg Expression formula C ₉ H ₁₂ O ₂ Infrared absorption spectrum (cm ^-1 )
3090, 3020, 1775, 16421610 Nuclear magnetic resonance spectrum (ppm)
1.70-2.66 (4H, m) 1.85 (3H, s) 4.09 (2H, s) 4.70-5.06 (1H, m) 5.56 (1H, dd, J = 6.16Hz) Production example 1 Metallic magnesium (24g) in the reaction vessel and ether (100 ml), add a catalytic amount of iodine and ethyl bromide, and stir vigorously. When the color of iodine disappears, cool it with ice water and monotonic salt, and add a solution of methallyl chloride (100 g) and ether (350 ml) to 0-8℃.
Make and drip. After the addition is complete, the mixture is further stirred at 10-13°C for 1 hour. Then, cool again and add a solution of furfural (91 g) and ether (100 ml) to
Add dropwise at °C. After the dropwise addition is complete, gradually return to room temperature and stir for approximately 1.5 hours. The reaction mixture is thoroughly cooled, diluted sulfuric acid is added to quench the reaction, and the mixture is extracted with ether. After washing the organic layer with saturated sodium bicarbonate solution and brine, the ether was distilled off at normal pressure. Distillation of the residue yielded 69 g of a pale yellow liquid, 3-methyl-1-furyl-3-buten-1-ol (boiling point 98-102°/14
mmHg, yield: 47.8%). Next, the above furan derivative (69 g) was added to the reaction vessel.
and ethanol (150 g), and concentrated hydrochloric acid (2.1 g) was added dropwise at room temperature. The reaction temperature is gradually increased from room temperature to 45°C over 30-45 minutes. Raise the temperature to 70℃ for another 1.5 hours, then continue to 70~
Stir at 80°C for 2 hours. The reaction mixture is cooled to 18°C and neutralized with dilute aqueous caustic soda solution. The mixture is extracted with toluene, and the organic layer is washed with saturated sodium bicarbonate solution and brine, and then concentrated under reduced pressure. The residue was distilled under reduced pressure to yield 41 g of ethyl-7-methyl-4-keto-7-
Octenoate is obtained as a pale yellow liquid.
(boiling point 121-128℃/10mmHg, yield 46%) Next, add the above ketoester (20g) to the reaction vessel.
Weigh out a 20% caustic soda aqueous solution (30 g), gradually raise the reaction temperature, and stir at 70-75°C for 1 hour. The mixture is cooled to 10° C. and a 1% caustic soda solution of sodium borohydride (1.5 g) is added dropwise. After the addition is complete, remove the ice bath and stir at room temperature for 1 hour. Pour the mixture into 50ml of water and extract with toluene to remove the oil. The aqueous layer is made acidic with dilute sulfuric acid and extracted with toluene. After washing the organic layer with brine, it is concentrated under reduced pressure. The residue was distilled under reduced pressure to obtain 7.5 g of the compound as a colorless and transparent liquid (yield 50%). In addition, the compound (15 g), p-toluenesulfonic acid (1 g) and toluene (50 ml) were placed in a reaction vessel, the reaction temperature was gradually raised, and the mixture was stirred under reflux for 1 hour. The mixture was cooled to room temperature, washed with brine, concentrated under reduced pressure, and the residue was distilled under reduced pressure to obtain 15 g of the compound as a colorless transparent liquid. (yield
100%) Next, the compound (5.0g) and carbon tetrachloride (40ml)
Weigh out sulfuryl chloride (7.0g) at 5-15℃.
Slowly drip. After the addition was completed, the mixture was stirred at 20°C for 2 hours, and the reaction mixture was poured into ice water. After extraction with carbon tetrachloride, the organic layer was washed with water, washed with 2.5% sodium bicarbonate solution, further washed with brine, and concentrated under reduced pressure to yield 7-methyl-6-chloro-4-hydroxy-7.
-Octenoic acid lactone is obtained. Then, put this chlorolactone (6g) and toluene (30ml) in a reaction container.
Weigh it out and gradually heat it with a mantle heater. Stop heating when the temperature reaches about 40℃, and
A solution of diazabicyclo[5.4.0]undec-7-ene (7 g) and toluene (10 ml) is added dropwise.
After the dropwise addition was completed, the mixture was refluxed for 2 hours to complete the reaction. Cool the mixture well and wash with dilute hydrochloric acid. Then, after washing with water,
Concentrate under reduced pressure and distill the residue under reduced pressure to obtain 1 g of the compound as a colorless liquid. (Yield 20%) Tables 2 and 3 show the compounds and their physicochemical and spectroscopic data. The compound and the method for synthesizing the compound are described in Production Example 1, so their description will be omitted. Table 2 (Compound) Apparent properties Colorless liquid Boiling point 124-128℃/10mmHg Expression formula C ₉ H ₁₄ O ₂ Infrared absorption spectrum (cm ^-1 )
3095, 1780, 1650, 895 nuclear magnetic resonance spectrum (ppm)
1.62-2.65 (8H, m) 1.73 (3H, s) 4.20-4.70 (1H, m) 4.70 (2H, s) Table 3 (Compound) Apparent properties Colorless liquid Boiling point 125-128℃/10mmHg Indicative formula C ₉ H ₁₄ O ₂ infrared absorption spectrum (cm ^-1 ) 3040, 1780 Nuclear magnetic resonance spectrum (ppm) 1.65 (3H, s) 1.73 (3H, s) 1.67-2.63 (6H, m) 4.17-4.64 (1H, m) 5.12 (1H, t, j = 7 Hz) Table 4 shows the physicochemical and spectroscopic data of the compound, and its synthesis method is described as Production Example 2. Table 4 Apparent properties Colorless liquid Boiling point 125-127℃/10mmHg Signal formula C ₉ H ₁₄ O ₂ Infrared absorption spectrum (cm ^-1 ) 1770, 2830, 1175 Nuclear magnetic resonance spectrum (ppm) 0.94 (6H, d ) 1.7-2.8 (5H, m) 4.0-4.5 (1H, m) 5.4 (1H, m) 5.5 (1H, m) Production example 2 Malonic acid, monoethyl ester (53
Weigh g) and methylene chloride (140ml), add THF
Into the solution, a Grignard reagent prepared from isobutyl bromide (61 g) and magnesium metal (12 g) was added dropwise. Stop dripping when propane gas is no longer generated. At this time, the reaction temperature rises to around 40-50°C. The reaction solution was cooled in an ice water-salt bath, and a solution of acid chloride (26.5 g) and methylene chloride (60 ml) was added dropwise. After the addition is complete, remove the ice bath and stir for 10 minutes. The mixture is cooled to below 0°C, 10% aqueous hydrochloric acid solution (600 g) is added, and when carbon dioxide has ceased to be generated, it is extracted with methylene chloride. The organic layer was washed with aqueous sodium bicarbonate and brine, concentrated under reduced pressure, and the residue was distilled under reduced pressure to obtain 26 g of ethyl-6-methyl-3-keto-4-heptenoate as a colorless and transparent liquid (boiling point: 112-114 ℃/15 mmHg, yield 71%) Next, the above ketoester (20 g) and ethanol (30 g) were added to sodium ethoxide prepared from metallic sodium (2.5 g) and ethanol (150 ml).
ml) solution was added dropwise at 10-18°C and incubated for an additional 30 minutes at 15-18°C.
Dropwise at 20℃, followed by sodium iodide (1
Add g). Gradually raise the reaction temperature and keep under reflux for 7
Stir for an hour. After the reaction is completed, ethanol is distilled off, 80 g of 15% caustic soda aqueous solution is added to the residue, and the mixture is stirred at 70-80°C for 1.5 hours to carry out hydrolysis and decarboxylation reactions. The mixture is then cooled in an ice-water bath, sodium borohydride (2 g) is added dropwise at 5°C, and the mixture is further stirred at 20-30°C for 2 hours. Pour the reaction mixture into well-chilled dilute sulfuric acid, make sure it has become slightly acidic, and extract toluene. After washing the organic layer with brine, it is concentrated under reduced pressure. The residue was distilled under reduced pressure to obtain 7 g of a colorless and transparent compound (yield 41.3%). Next, the effect when the compound of the present invention is blended into a fragrance composition will be explained. Example 1 A peach fragrance was prepared by blending the following ingredients. (Weight ratio) 95% ethanol 418.5 parts Propylene glycol 350.0 Gamma hexalactone 10.0 Gamma octalactone 11.0 Aldehyde C ₁₈ 9.5 Gamma decalactone 38.0 Delta decalactone 10.0 Cis-3-hexenol 10.0 Trans-2-hexenol 80.0 Normal-hexanol 12.0 Hexyl acetate 11.0 Cis-3-hexenyl acetate 14.0 2-methylbutyric acid 3.5 Trans-2-hexenal 2.0 Compound 2.5 1000.0 parts The above fragrance composition was used as a "sample", and a "control" prepared by adding 2.5 parts of propylene glycol instead of the compound 3 by a panel of 19 fragrance experts.
A discrimination test was conducted using the point comparison method to compare and evaluate the aroma. As a result, an 18-member panel found the ``sample'' to be better than the ``control,'' noting that it had a strong peach ripeness. Example 2 A vanilla fragrance was prepared by blending the following ingredients. (Weight ratio) Vanilla tincture 850 parts Vanillin 60 Ethyl vanillin 20 Cyclotene 10 Maltol 6 Compound 0.5 Compound 1.0 95% ethanol 52.5 1000.0 parts The above fragrance composition was used as a "sample", and the compounds,
When comparing the aroma with the "control" prepared by adding 1.5 parts of 95% ethanol instead of the "sample" using the panel of Example 1, 18 panelists found the "sample" to be better than the "control" and found it to be natural-like. He pointed out that his strength was clearly visible. Example 3 A butter flavor was prepared by blending the following ingredients. (Weight ratio) Delta decalactone 14 parts Deltawn decalactone 20 Delta decalactone 24 Ethyl myristate 9 Diacetyl 1.4 Acetoin 1.0 Ethyl pyruvate 0.3 2-heptanone 0.2 Ethyl levulinate 0.2 2-nonanone 0.3 Normal propyl levulinate 0.1 Compound 2.5 Compound 4.5 Triacetin 922.5 1000.0 parts The above fragrance composition was used as the "sample", and the compound,
When the aroma was compared with the "control" prepared by adding 7 parts of triacetin instead of the sample using the panel of Example 1, 18 panelists found the "sample" to be better than the "control", indicating that it had a natural butter feel. He pointed out that it appears strongly. Example 4 A tobacco fragrance was prepared by blending the following ingredients. (Weight ratio) Vanillin 20 parts Ethyl vanillin 4 Maltol 0.5 Cinnamon oil 22.0 Menthol 5 Perbalsam 7 Aldehyde C ₁₆ 6 Ethyl propionate 4 Ethyl butyrate 5 Ethyl-2-methylbutyrate 7 Compound 0.3 Compound 0.1 95% ethanol 919.1 1000.0 parts Using the above perfume composition as a "sample", the compound and a "control" prepared by adding 0.4 parts of 95% ethanol instead were evaluated for aroma using the same panel as in Example 1, and 18 panelists answered "control". The "sample" is better, the amount of smoke increases in terms of aroma and taste, sweetness,
He pointed out that the plumpness is doubled. Example 5 A rose fragrance was prepared by blending the following ingredients. (Weight ratio) Better fuel Eleethyl alcohol 90 gelaniol 400 Rose oil bulba 100 Alf Ayonon 40 linerol 15 gelanille oil 60 gelanium oil 60 nerolol 200 rosini leh mate 20 dodecanal 2 dodecanal 2 Vanlynlin 5 compound 7 1000 parts The fragrance composition was used as a "sample" and the aroma was compared with a "control" prepared by adding 4 parts of triethyl citrate instead of the compound, using the same panel as in Example 1. All panel members are “controls”
The width of the natural rose is better than the "specimen",
He pointed out that depth and strength will emerge.

Claims (1)

[Scope of Claims] 1. An octanoic acid lactone represented by the following general formula [Formula] where R is an alkyl group having one or two straight chain double bonds of 4 carbon atoms and having a methyl group at the γ-position. 2. A fragrance composition characterized by containing an octanoic acid lactone represented by the following general formula. [Formula] However, R is an alkyl group having one or two straight chain double bonds having 4 carbon atoms and having a methyl group at the γ-position.