JPS6240329B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to aroma and/or flavor compositions. More particularly, the present invention relates to fragrance and/or flavor compositions comprising theaspiran as an essential aroma-imparting and/or flavor-imparting ingredient. Theaspiran [2.
6,10,10-tetramethyl-1-oxa-spiro[4,5]-dec-6-ene]
letters”, 1995 (1969), and is a known compound. This compound has special organoleptic properties,
It has been found according to the invention that they are particularly suitable as aromatizing and/or flavoring substances. In fact, theaspiran is found in very small concentrations in various essential oils, such as raspberry oil or yellow passion fruit oil [Helv.Chim.
Acta 57 , 1301 (1974); 55 , 1916 (1972);
54 , 1881 (1971)]. However, it is surprising that theaspiran has been found to be highly suitable as an aromatizing and/or flavoring substance. This is because none of the above publications mention anything about the special sensory properties of theaspiran. The present invention therefore provides in one aspect to this, a fragrance composition comprising as an essential aromatizing and/or flavoring ingredient theaspiran (excluding naturally occurring mixtures containing theaspiran), practically pure or in a mixture; (or) relating to flavor compositions. Practically pure theaspiran specifically refers to theaspiran which does not contain any accompanying substances other than theaspiran in the above-mentioned natural oil extraction. Practically pure theaspiran within the scope of the present invention includes, for example, synthetically produced theaspiran. Theaspiran used according to the invention as aromatizing and/or flavoring substance is notable for its particular fresh fruity aroma or flavour. Of particular interest are the berry-like, green notes and the sweet, mellow nuances that develop as the concentration increases. Therefore, theaspiran is used for aromatizing or flavoring various products such as cosmetics (soaps, ointments, face powder, etc.), detergents, foods, luxury goods and beverages, but theaspiran is not used alone and can be used to impart other fragrances. Preferably, it is used in the form of a composition containing substances or flavoring substances. In another respect, the present invention provides for substantially pure or mixed (other than natural mixtures containing theaspiran)
by adding theaspiran to known aroma and/or flavor compositions or by mixing the theaspiran with natural or synthetic compounds or mixtures thereof suitable as components of the aroma and/or flavor compositions. , relates to a method for producing aroma compositions and/or flavor compositions. Since theaspiran has a pronounced natural note, it is particularly suitable as an odorant for modifying known compositions, such as those of the chypre type.
For example, it is extremely suitable for combinations with flower notes such as neroli and rose notes. The concentration of theaspiran in the composition can vary within a wide range depending on the intended use. For example, a range of about 1% by weight (in detergents) to about 15% by weight (as alcoholic solutions) can be used. With perfume bases or concentrated oils, the concentration will of course be higher. Theaspiran as a flavoring substance can be used, for example, to produce or improve fruit and berry flavors in foods (such as yoghurt and cakes), luxury goods (such as cigarettes) and beverages (such as lemonade).
Can be used to enhance or modify. The remarkable flavor properties of virtually pure, especially synthetically produced, theaspiran allow it to be used in low concentrations. The appropriate amount thereof is preferably 0.00001ppm to 1ppm in the final product, i.e. aromatized food, luxury food or beverage.
It is within the range of 0.001ppm to 0.1ppm. Some of the effects produced using theaspiran are summarized in the following table.

TABLE Theaspiran can be mixed with the ingredients used in flavor compositions or added to such flavorants in a conventional manner. Flavorants used according to the present invention refer to flavor compositions that can be diluted or dispersed in food products in a known manner. These flavorants can be converted by known methods into the customary forms of use, such as solutions, pastes or powders. The product can be spray dried, vacuum dried or freeze dried. When preparing the above-mentioned usual usage forms, mention may be made of the following substances such as carrier substances, thickeners, flavor improvers, and auxiliary ingredients. gum arabic, gum tragacanth, salts or brewer's yeast, alginic acid, carrageenan or similar absorbents, indoles, maltol, dienals, spice oleoresins, tobacco flavors,
Cloves, diacetyl, sodium citrate, monosodium glutamate, disodium inosine-5'-monophosphate (IMP), disodium guanosine-5-phosphate (GMP), special flavoring substances, water, ethanol, propylene glycol and Glycerin. As can be seen from the foregoing description, it is within the scope of the present invention to use the aromatic and/or flavor compositions already mentioned, or theaspiran (excluding naturally occurring mixtures containing theaspiran) in virtually pure or mixed form. It also includes methods of imparting aroma and/or flavor to a substance by applying or adding it to the substance. The present invention further provides formula 4 in the reaction scheme diagram below.
The present invention relates to a new method for producing theaspiran, which comprises treating -(2,6,6-trimethyl-2-cyclohexen-1-ylidene)-butan-2-ol with an acid. Particularly suitable acids include protic acids such as inorganic and organic protic acids (i.e. sulfuric acid, phosphoric acid, p
-toluenesulfonic acid, etc.) or Lewis acids ( _BF3 , _SnCl4 , ZnCl2 _, etc.). p-Toluenesulfonic acid is a preferred protic acid. To cyclize 4-(2,6,6-trimethyl-2-cyclohexen-1-ylidene)-butan-2-ol of the formula to theaspiran of the formula,
It can be carried out with or without a solvent. Suitable solvents include inert solvents such as hexane,
These are benzene, nitromethane, chlorinated hydrocarbons (such as chloroform) and ethers (such as dioxane). Benzene and toluene are suitable solvents. The reaction temperature is not critical, and the above treatment can be carried out at room temperature, as well as at higher or lower temperatures. It is known in the art to oxidize theaspiran in the following scheme to produce the flavoring substance theaspiran of the formula (e.g. U.S. Pat.
3645755), it can be said that the method of the present invention is also an advantageous way to reach theaspiran. A method of producing theaspiran by oxidizing theaspiran (produced according to the method described above) by known methods also forms part of the present invention.

[Table] Regarding the above reaction diagram, the alcohol of the formula can be obtained from the acyloxy compound of the formula,
This compound is obtained from the formula β-ionone.
An acyloxy compound of the formula can be converted to an alcohol of the formula using, for example, a complex hydride such as lithium borohydride, sodium borohydride, potassium borohydride, lithium aluminum hydride.
The reaction is advantageously carried out in alcohols such as alkanols, alcohol-ether mixtures or ethers as solvent. The reaction temperature is not critical, but it is preferably carried out at a temperature of about -10°C to 80°C. The acyloxy compound of the formula can be obtained by reacting the β-ionone of the formula with enol acylate.
Suitable enol acylates include isopropenyl acetate, isobutenyl acetate, and the like. The production of acyloxy compounds of the formula is advantageously carried out in the presence of a catalytic amount of an acid, such as any of the acids mentioned above. p-Toluenesulfonic acid is a preferred acid. It is advantageous to use an excess of enol acylate, this compound also acting as a solvent. This reaction is preferably carried out at the reflux temperature of the reaction mixture, and the ketone (acetone in the case of isopropynyl acetate) formed during the reaction is continuously distilled off. The formula includes four possible stereoisomers,
It will be understood that the formula includes a total of four stereoisomers. Similarly, formula and formula include two diastereomeric compounds (ie, two pairs of enantiomers). The following examples are intended to illustrate the invention. Example 1 (Reference example) 96g of β-ionone and 500ml of isopropenyl acetate
Dissolved in p-toluenesulfonic acid monohydrate 0.6
It was treated with g. The mixture was stirred at reflux temperature for 24 hours under an inert gas atmosphere. Excess isopropenyl acetate is distilled off from the reaction mixture under vacuum (temperature ≤
50°), then treated the mixture with hexane several times,
The remaining isopropenyl acetate was removed and concentrated again. In this way, the reddish-brown 4-(2, 6, 6
-trimethyl-2-cyclohexen-1-ylidene)-2-acetoxy-but-2-ene (formula,
108 g of R=acetyl were obtained. UV absorption (ethanol): λ _nax = 276 nm, logε
=4.265. IR absorption (film): 1755, 1650, 1580,
1370, 1220/1205, 1150/1140, 1040, 1020,
945, 925, 885/875/865, 818cm ^-1 . NMR absorption (CDCl ₃ + TMS): δ = 6.65−5.85
(2H, m), δ=5.78 (1H, broad t), δ=
2.20 and 2.15 (3H, s each), δ = 2.05
(3H, broad s), δ=1.85 (3S, narrow m), δ=1.28ppm (6H, s). MS (mass spectrometry): m/e: 234, fragment
192, 177, 159, 149, 136, 121, 107, 91,
81, 77, 71, 65, 55, 43 = basic peak, The obtained crude acetoxy compound (108 g) shown by the formula was dissolved in 400 ml of 96% ethanol, and then
Sodium borohydride in 600ml of 96% ethanol
It was added dropwise to 20 g of suspension within 10 minutes at 20-30° C. with slight cooling. The mixture was then heated to slight reflux and stirred at this temperature for 15 minutes. The end of the reaction can be detected by a color change from deep yellow to lemon yellow. The cloudy mixture, cooled to room temperature, was poured into a saturated ammonium chloride solution-ice mixture and extracted with hexane. After washing until neutral with regular water washing and drying over anhydrous sodium sulfate, the solvent was evaporated in vacuo. Coarse 4-
(2,6,6-trimethyl-2-cyclohexen-1-ylidene)-butan-2-ol (formula)
Obtained 96g. UV absorption (ethanol): λ _nax : 239 nm (logε
=4). IR absorption (film): 3300, 1380/1370/
1360, 1125, 1085, 950, ^{880, 830cm -1} . NMR absorption (CDCl ₃ +TMS): δ = 5.7 (1H, broad t), δ = 5.4 (1H, t and J = 7Hz),
δ=3.9 (1H, m and J=6Hz), δ=2.55
(2H, broad t and J=7Hz), δ=1.85
(3H, narrow m), δ=1.25 (3H, d and J
= 6Hz), δ = 1.23ppm (6H, s). MS: m/e: 194, fragments 189, 161,
150, 135 = basic, 121, 107, 93, 79, 69, 55,
45, 41. 96 g of the crude alcohol of the formula was mixed with 1.3 g of anhydrous benzene in the presence of 1 g of p-toluenesulfonic acid monohydrate.
The mixture was heated under reflux for 10 hours. The solution was poured into a cold saturated solution of bicarbonate and extracted with hexane. The extract was washed until neutral, dried over sodium sulfate, and then the solvent was evaporated in vacuo. 96 g of crude theaspiran as a brown oil of the formula were separated from the first run and the residue by short condenser distillation. Yield: 77g of theaspiran of the formula, boiling point = 75℃/0.2mmHg, n _D ²⁰
=1.492. IR absorption (film): 1475, 1455, 1380,
1360, 1285, 1195, 1160/1150, 1130, 1110/
1085/1080/1060, 1040, 1005, 990, 975,
930, 910/900, 880, 825, 775, 725cm ^-1 . NMR absorption (CDCl ₃ + TMS): Isomer A δ = 5.25 (1H, narrow m), δ = 4.1 (1H, broad m), δ = 1.75 (3H, narrow m), δ =
1.26 (3H, d and J = 6 Hz), δ = 0.95 and 0.88 ppm (3H, s, respectively). Isomer B δ = 5.40 (11H, narrow m), δ = 4.05 (1H,
Broad m), δ=1.7 (3H, narrow m), δ=
1.28 (3H, d and J = 6 Hz), δ = 1.00 and 0.88 ppm (3H, s, respectively). MS: m/e: 194, fragments 179, 151,
151, 135 = basic peak, 123, 109, 96, 82,
77, 67, 55, 41. Example 2 (Reference Example) Dissolve 5.7 g (30 mmol) of theaspiran in 60 ml of anhydrous tertiary butanol, and dissolve 120 ml of t-butylchromate solution [150 g of CrO ₃ , 400 ml of tertiary butanol, and 140 ml of acetic anhydride] (approximately 30 mmol of _t -butyl chromate). (equivalent to mmol) at 40° C. within 2 hours.
This mixture was then stirred at 40°C. Another 20 ml of t-butyl chromate solution was added dropwise after 8 days.
The same amount was added a day later. The treatment of the mixture was completed after a total of 16 days. This mixed solution was added to 1 part of methylene chloride, which was covered with ice, and 1 part of a mixed solution of sulfite and bisulfite [40 g of sodium bisulfite, 50 g of sodium sulfite, 1 part of water] was added and stirred for 1 hour. The mixture was then washed with a foaming sodium bicarbonate solution until neutral, then water, dried over magnesium sulfate and evaporated to dryness. 3.0 g of a yellow oil was obtained, which was purified by column chromatography on 30 volumes of silica gel (particle size 0.063-0.200 mm) using a hexane/ether mixture containing 5-10% ether. boiling point
The yield of theaspiran at 88°C/0.12mmHg was 20%. UV absorption (ethanol): λ _nax = 235 nm (ε =
11740). MS: m/e: 208=M+, 193, 175, 152 , 110,
96, 82, 69, 55, 41. IR absorption (film): 1675 , 1630 , 1480 ,
1450 , 1390/80/70, 1345, 1310, 1280,
1270, 1160, 1090 , 980, 920, 890cm ^-1 . NMR absorption (CDCl ₃ + TMS): at δ=5.72
1H (narrow quartet and J=1.5Hz), δ=4.2
1H (multiple line) at ° (center position), δ=
3H (single line for each of the two diastereomers) at 2.01 and δ = 1.99, δ =
3H (double and J=6Hz) at 1.30, δ
= 6H at 0.99 and 1.02 (single line for paired dimethyl groups). Example 3

Table: Composition B had a much stronger fruity aroma than Composition A and also retained its tack substantially longer than Composition A. Example 4

[Table] Composition B was organoleptically different from Composition A, a traditional vanilla aroma, and was highly advantageous. In particular, theaspiran significantly softened the vanilla fragrance as it imparted a weak, dull, fruity note. Example 5

【table】

[Table] A B
Theaspiran (1% ethanol solution) - 10

Claims (1)

[Claims] 1. An aromatic and flavoring agent characterized in that it contains theaspiran in practically pure form or in the form of a mixture (excluding theaspiran-containing natural mixtures), as well as other known odor-imparting and flavor-imparting ingredients. (or) a flavor-improving, enhancing, promoting or modifying composition. 2 Containing synthetically produced theaspiran,
A composition according to claim 1.