JP2016124833A - 2(e),8(z)-tetradecadiene-1-al and perfume composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel perfume material capable of adding or enhancing natural feeling to citrus aroma and flavor.SOLUTION: There is provided 2(E), 8(Z)-tetradecadiene-1-al represented by the following formula (1) and a perfume composition containing the same as an active ingredient. There is provided the perfume composition containing 5 ppb to 10% of 2(E), 8(Z)-tetradecadiene-1-al.EFFECT: The 2(E), 8(Z)-tetradecadiene-1-al exhibits unique green note, flavedo-like, fruit-like and resin-like aroma and can add and enhance natural feeling or flesh feeling to citrus aroma and flavor even with small amount of addition.SELECTED DRAWING: Figure 1

Description

  The present invention has novel compounds 2 (E), 8 (Z) having a green note and a flavedo-like fragrance peculiar to fresh citrus fruits and having an action of imparting or enhancing a natural feeling or freshness to a citrus fragrance and flavor. ) -Tetradecadiene-1-al and a fragrance composition containing the same.

  Regarding fragrance components of citrus fruits, oxygen-containing compounds such as hydrocarbons such as limonene and myrcene, aldehydes, alcohols and esters have been found so far as main fragrance components. In particular, octanal, nonanal, decanal, dodecanal, neral, geranial and sinensal, which are aldehydes, and linalool, which is an alcohol, are important and are used as perfume materials.

  In recent years, as consumer preferences have diversified, perfume compositions blended in citrus-based foods and beverages, cosmetics, and the like have been demanded to be more natural and natural. However, it has been difficult to reproduce such a natural citrus flavor only by combining conventionally known aroma components. For this reason, various techniques for imparting or enhancing a natural feeling to citrus flavors have been proposed. For example, (Z) -pentadecenal (Patent Document 1), 4,5-epoxy-2E-decenal (patents) Document 2), 8-tetradecenal (Patent Document 3), prenyl ethyl ether (Patent Document 4) and the like are disclosed. However, even with these technologies, it is difficult to say that the demands of consumers are fully met.

JP 2014-43409 A JP 2009-82048 A JP-T-2004-534147 JP-A-2005-204617

  This invention is made | formed in view of the said situation, and makes it a subject to provide the novel fragrance | flavor raw material which can provide or enhance the natural feeling to citrus-type aroma and flavor.

  The present inventors found that freshly harvested citrus fruits have a unique green note and flavedo-like fragrance, and reproduction of this part is necessary to impart or enhance a natural feeling in citrus aroma and flavor. I thought it was important. Therefore, we proceeded with detailed analysis on Citrus pseudogulgul Hort. Ex Shirai, which has a unique green note and flavedo-like fragrance, and as a component contributing to the fragrance, 2 (E), 8 It was found that (Z) -tetradecadiene-1-al exists. And, in addition to the unique green note and flavedo-like fragrance, the compound has a fruit-like fragrance, and when added to the fragrance composition, it is found that the natural feeling of citrus fruits can be imparted and enhanced, and the present invention is completed. It came to do.

  That is, the present invention is 2 (E), 8 (Z) -tetradecadien-1-al and a fragrance composition containing this as an active ingredient.

  Moreover, this invention is the food / beverage containing the said fragrance | flavor composition.

  The 2 (E), 8 (Z) -tetradecadiene-1-al of the present invention exhibits a unique green note, flavedo-like, fruit-like and fat-like aroma, and even with a small addition amount, citrus aroma and flavor. A natural feeling or a fresh feeling can be imparted to or enhanced. Furthermore, palatability can be remarkably improved by suppressing the oily part which gives an artificial impression, or adjusting the fragrance balance.

It is a figure which shows the mass spectrum of 2 (E), 8 (Z) -tetradecadien-1-al.

  2 (E), 8 (Z) -tetradecadien-1-al of the present invention is a compound represented by the following formula (1). There is no report and synthesis example that the compound has been separated from natural products so far, and it is a novel compound. The present inventors have isolated the compound for the first time from Citrus pseudogulgul Hort. Ex Shirai pericarp as a component contributing to a unique green note and flavedo-like aroma. Therefore, the compound can be obtained by separating and purifying from pericarp peel according to a conventional method, but can also be produced by chemical synthesis.

The method for synthesizing 2 (E), 8 (Z) -tetradecadien-1-al is not particularly limited, and can be synthesized using a general organic chemical reaction. It can be produced according to a synthetic scheme. In this scheme, first, triphenylphosphonium salt (3) is synthesized from ethyl 6-bromohexanoate (2) and triphenylphosphine (step 1). Next, ethyl 6 (Z) -dodecenoate (4) is obtained by Wittig reaction with hexanal (step 2), and this is converted to 6 (Z) -dodecenol (5) by hydride reduction (step 3). Further, 6 (Z) -dodecenal (6) was obtained by desmartin oxidation (step 4), and then 2 (E), 8 (Z) -tetradecadiene- by a Wittig reaction with (triphenylphosphoranylidene) acetaldehyde. 1-R (7) can be obtained (Step 5).

  The 2 (E), 8 (Z) -tetradecadien-1-al thus obtained has a unique pericarp green note, flavedo-like, peach-like, melon-like and fat-like scent. 2 (E), 8 (Z) -tetradecadien-1-al is directly added to food and drink, pharmaceuticals, quasi drugs, cosmetics, detergents, fragrances, etc. The fragrance / flavor can be imparted or enhanced, but the fragrance composition is prepared by mixing with other fragrance ingredients, etc., in addition to food and drink, pharmaceuticals, quasi-drugs, cosmetics, detergents, It can be blended with various toiletry products such as fragrances to give or enhance a citrus fragrance or flavor with a natural or fresh feeling.

  In the fragrance composition of the present invention, as other fragrance components that can be formulated with 2 (E), 8 (Z) -tetradecadien-1-al, hydrocarbons, alcohols, phenols, aldehydes, ketones Synthesis, natural fragrances, natural essential oils, plant extracts, animal extracts, etc. of these, acetals, ethers, esters, lactones, sulfur-containing compounds, nitrogen-containing compounds, etc. Species or two or more can be used. Among these, the use of a fruit-based fragrance component, particularly a citrus-based fragrance component, is preferred because the citrus aroma and the natural and freshness of the flavor are emphasized and a flavor that captures the characteristics of natural citrus fruits. Examples of such citrus perfume ingredients include terpene hydrocarbons such as limonene, myrcene and terpinene, aldehydes such as octanal, decanal and geranial, terpene alcohols such as linalool, citronellol and terpineol, oranges, grapefruits and lemons. , Natural essential oils obtained by cold-pressing or steam-distilling citrus peels such as limes, bergamots and yuzus, terpene-less oils from which terpenes have been removed, distilled concentrates, fruit juices, etc. The essence oil, aroma, etc. which are collected at the time of a fraction are illustrated.

  The content of 2 (E), 8 (Z) -tetradecadien-1-al in the fragrance composition of the present invention is not particularly limited, but is usually 5 ppb to 100,000 ppm in the fragrance composition, preferably It is 10 ppb to 1000 ppm, more preferably 100 ppb to 100 ppm. Within such a range, the natural feeling of citrus aroma and flavor is enhanced and the palatability is high.

  On the other hand, the content of the citrus fragrance component in the fragrance composition of the present invention is not particularly limited, but is usually 0.00001 to 99.99999 mass% in the fragrance composition, preferably 0.2 to It is 99 mass%, More preferably, it is 2-99 mass%.

  In the fragrance composition of the present invention, additives such as commonly used solvents, retention agents, adjuvants, harmony agents, modulators, excipients and the like can be blended as necessary.

  The fragrance composition of the present invention can be blended in various toiletry products such as quasi-drugs, pharmaceuticals, cosmetics, detergents and fragrances in addition to food and drink. Examples of foods and beverages include fruit juice beverages, fruit liquors, sports beverages, carbonated beverages, tea beverages, lactic acid bacteria beverages, sparkling liquors, distilled liquors, mixed liquors, etc .; ice cream, ice confectionery, yogurt, pudding, jelly, etc. Desserts; cakes, dumplings, chewing gum, hard candy, gummy candy and other confectionery in general; processed fruit products such as fruit flavor sauces and jams; condiments such as dressing, ponzu, sauce and soup; Japanese-style soups, Western-style soups And soups; instant foods; various snack foods; processed products such as koji paste products, retort foods, pickles, boiled foods, prepared dishes, frozen foods, etc. Although the addition amount of this invention fragrance | flavor composition in food / beverage products is not specifically limited, Usually, 0.0005-2 mass% in food / beverage products, Preferably 0.005-0.5 mass%, More preferably, it is 0.05-0.2 mass%. The content of 2 (E), 8 (Z) -tetradecadien-1-al in the fragrance composition is usually 0.005 ppb to 50 ppm, preferably 0.05 ppb to 0.5 ppm in the food and drink. Preferably, it is 0.5 ppb to 0.05 ppm.

  The amount added when the fragrance composition of the present invention is used as a fragrance component such as pharmaceuticals, quasi-drugs, cosmetics, detergents, and fragrances may be appropriately set according to the purpose and the like. 00001-99.9999 mass%, preferably 0.0001-50 mass%, more preferably 0.001-30 mass%, and 2 (E), 8 (Z) -tetradecadien-1-al, 0.005 ppb to 50000 ppm, preferably 5 ppb to 500 ppm, more preferably 50 ppb to 50 ppm.

  On the other hand, when 2 (E), 8 (Z) -tetradecadiene-1-al is added to a food or drink as it is, 2 (E) or 8 (Z in the food or drink as in the case of the fragrance composition. ) -Tetradecadien-1-al content is usually 0.005 ppb to 50 ppm, preferably 0.05 ppb to 0.5 ppm, more preferably 0.1 ppb to 0.05 ppm. . The types of food and drink that can be blended are the same as in the case of the fragrance composition. Moreover, the addition amount and kind when adding to cosmetics etc. are the same as that of the case of a fragrance | flavor composition.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, this invention is not limited to these at all.

Reference example 1
Isolation of 2 (E), 8 (Z) -tetradecadien-1-al from Shishizu:
The flavedo portion of shizuyuzu fruit (2860 g) was peeled off with a knife, and the flavedo (980 g) was soaked in methylene chloride (1600 ml) and allowed to stand at room temperature for 2 hours. Thereafter, the solid matter was removed by filtration, and sodium sulfate was added for dehydration. Methylene chloride was distilled off under reduced pressure to obtain shiizu peel essential oil (14.8 g). A part of the obtained essential oil was subjected to GC and GC-MS analysis. Aroma extract dilution analysis (AEDA) method was used to search for aroma contribution components. The essential oil was diluted 2 ⁿ times in order with ethanol, and 1.0 μl of each was splitless injected for GC-O analysis. Aromagram was prepared from the obtained Flavor dilution (FD) value. The essential oil obtained above was fractionated by silica gel column chromatography to examine a trace amount of components contributing to aroma. 1.59 g of essential oil was applied to a silica gel column (17 × 1.6 cm), fraction 1 (pentane), fraction 2 (pentane: diethyl ether = 97: 3), fraction 3 (pentane: diethyl ether = 90: 10), When the fraction was divided into fraction 4 (diethyl ether) and each fraction was concentrated and analyzed by GC-O, a flavedo-like aroma was strongly detected in fraction 3. When fraction 3 was further subjected to GC-O-MS analysis, a mass spectrum of an unknown component was obtained. This unknown component was isolated using a GC-PFC apparatus. This was subjected to hydride reduction to obtain an alcohol, and then a mass spectrum was obtained by GC-MS. The position of the unsaturated double bond was estimated from the analysis result of this mass spectrum, and the unknown component was estimated to be 2 (E), 8 (Z) -tetradecadien-1-al. Since 2 (E), 8 (Z) -tetradecadien-1-al synthesized by the following reaction scheme was consistent with mass spectrum, retention time and odor quality, the unknown component was 2 (E), 8 (Z) -tetradecadien-1-al was identified.

Example 1
Synthesis of 2 (E), 8 (Z) -tetradecadien-1-al:
2 (E), 8 (Z) -tetradecadien-1-al was synthesized by the following reaction route. The percentage in parentheses below the process number indicates the yield of each process.

Step 1: Synthesis of Phosphonium Salt of Formula (3) In a 200 ml round bottom flask, 20.4 g (91.4 mmol) of ethyl 6-bromohexanoate, which is a compound of formula (2), and 20.0 g of triphenylphosphine (76 .3 mmol) and 38 ml of toluene were added, and the mixture was heated to reflux for 27 hours with stirring at normal pressure. After completion of the reaction, the organic layer was removed by decantation, the residue was washed with 100 ml of petroleum ether, and then the solvent was removed with a vacuum pump to obtain 36.7 g of a crude phosphonium salt of the formula (3).

Step 2: Synthesis of ester of formula (4) In a 200 ml round bottom flask, 36.7 g of crude phosphonium salt, 3.8 g (37.9 mmol) of hexanal, 12.6 g (91.2 mmol) of potassium carbonate, 0.684 g of water ( 37.8 mmol) and 1,4-dioxane (38 ml) were added, and the mixture was heated to reflux for 7 hours with stirring at normal pressure. To the reaction solution was added 300 ml of water, extracted with methylene chloride, dehydrated with sodium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (petroleum ether: diethyl ether = 40: 1) to obtain 7.28 g of a crude product. This crude product and 64 ml of ethanol were charged into a 100 ml eggplant flask, and 0.365 g of sodium borohydride was added thereto. After stirring at room temperature for 10 minutes, 10 ml of saturated aqueous ammonium chloride solution was added to the reaction solution to stop the reaction, and then ethanol was removed as much as possible under reduced pressure. 100 ml of water was added to the resulting residue, extracted with methylene chloride, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (petroleum ether: diethyl ether = 40: 1), and 5.49 g (24.0 mmol, 63% yield) of ethyl 6 (Z) -dodecenoate of the formula (4) 99% purity) was obtained.

Step 3: Synthesis of 6 (Z) -dodecenol of Formula (5) Under a nitrogen atmosphere, 2.3 g (60.6 mmol) of lithium aluminum hydride and 200 ml of tetrahydrofuran were added to a 500 ml round bottom flask and cooled to 0 ° C. . Thereto, 40 ml of a tetrahydrofuran solution containing 5.49 g (24.3 mmol) of ethyl 6 (Z) -dodecenoate was added dropwise over 5 minutes, followed by stirring at room temperature for 2 hours. The reaction solution was cooled again to 0 ° C., and 2.3 ml of water, 2.3 ml of 1M sodium hydroxide aqueous solution and 6.9 ml of water were sequentially added to stop the reaction with vigorous stirring. Thereto, 20 g of sodium sulfate was added, stirred for 30 minutes, filtered, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (petroleum ether: diethyl ether = 5: 1), and 3.54 g (18.9 mmol, yield 79%, purity 98) of 6 (Z) -dodecenol of formula (5). %).

Step 4: Synthesis of 6 (Z) -dodecenal of formula (6) In a 500 ml round bottom flask, 3.54 g (18.9 mmol) 6 (Z) -dodecenol, 192 ml methylene chloride and 12.2 g desmartin periodinane ( 28.8 mmol), and stirred at room temperature for 1 hour. The reaction solution was added with 100 ml of 1M aqueous sodium hydroxide solution and 30 ml of saturated aqueous sodium thiosulfate solution to stop the reaction, then added with 200 ml of water, extracted with methylene chloride, dehydrated with sodium sulfate, filtered, and then subjected to reduced pressure. Concentrated with. The resulting residue was purified by silica gel column chromatography (petroleum ether: diethyl ether = 30: 1), and 3.29 g (17.4 mmol, yield 92%, purity 97) of 6 (Z) -dodecenal of formula (6) %).

Step 5: Synthesis of 2 (E), 8 (Z) -tetradecadien-1-al of Formula (7) In a 200 ml round bottom flask, 2.80 g (15.4 mmol) of 6 (Z) -dodecenal, (tri Phenylphosphoranylidene) acetaldehyde (9.35 g, 30.7 mmol) and toluene (77 ml) were charged, and the mixture was heated and stirred at 80 ° C. for 9 hours. Concentration under reduced pressure, the resulting residue was purified by silica gel column chromatography (petroleum ether: diethyl ether = 100: 1), 2 (E), 8 (Z) -tetradecadiene-1 of formula (7) -1.72 g (7.1 mmol, crude yield 46%, purity 86%) were obtained. This was further purified by silica gel column chromatography (petroleum ether: diethyl ether = 200: 1), and 2 (E), 8 (Z) -tetradecadien-1-al 0.058 g (purity 94) of formula (7) %). FIG. 1 shows a GC-MS spectrum. The GC-MS and ¹ H-NMR spectrum analysis results are shown below.
(1) MS m / z (%): 41 (100), 55 (93), 67 (84), 81 (84), 95 (58), 109 (30), 123 (25), 137 (26) , 152 (19), 165 (6), 177 (2), 190 (1), 208 [M ⁺ ] (1)
(2) ¹ H-NMR (400 MHz, CDCl ₃ ), δ (ppm): 9.51 (d, J = 7.9 Hz, 1H), 6.85 (dt, J = 15.6 Hz, 6.8 Hz, 6.8 Hz, 1H), 6.12 (dd, J = 15.6 Hz, 7.9 Hz, 1H), 5.42-5.33 (m, 2H), 2.35 (td, J = 6.9 Hz) 7.4 Hz, 7.4 Hz, 2H), 2.08-1.99 (m, 4H), 1.65-1.48 (m, 2H), 1.44-1.39 (m, 2H) 1.37-1.23 (m, 6H), 0.88 (t, J = 6.9 Hz, 3H)

Example 2
Aroma evaluation of 2 (E), 8 (Z) -tetradecadien-1-al:
When the fragrance tone was evaluated for 2 (E), 8 (Z) -tetradecadien-1-al, it showed green notes, unique green notes, flavedo-like, peach-like, melon-like and fat-like odors. Moreover, it was 0.009 ppb as a result of investigating the threshold value of 2 (E), 8 (Z) -tetradecadien-1-al in water using a 5-point comparison method. That is, this material has been shown to have a sensory and detectable effect on the aroma and flavor of the composition even in small amounts.

Example 3
Preparation of perfume composition (1):
As an orange-like blended fragrance composition, a basic blended fragrance composition comprising the components shown in Table 1 below was prepared.

  An orange-like blended fragrance composition was prepared by mixing 100 g of the above composition with 0.005 g of 2 (E), 8 (Z) -tetradecadien-1-al produced in Example 1. 1 g of this blended fragrance composition was added to 1000 ml of water, and the filtered composition and 1 g of the above basic blended fragrance composition to which the compound was not added were added to 1000 ml of water. Compared. As a result, the blended fragrance composition to which the compound was added emphasized the natural feeling and freshness of citrus aroma and citrus flavor, and became a flavor that captured the characteristics of natural orange. Furthermore, it is a fragrance peculiar to the basic blended fragrance composition, and also exhibits an effect of suppressing an oily part that gives an artificial impression, etc., and is extremely excellent in terms of palatability.

Example 4
Preparation of fragrance composition (2):
As a lemon-like blended fragrance composition, a basic blended fragrance composition comprising the components shown in Table 2 below was prepared.

  A lemon-like blended fragrance composition was prepared by mixing 100 g of the above composition with 0.005 g of 2 (E), 8 (Z) -tetradecadien-1-al produced in Example 1. 1 g of this blended fragrance composition was added to 1000 ml of water, and the filtered composition was compared with 1 g of the above basic blended fragrance composition not containing the compound added to 1000 ml of water, and the flavor and flavor of the filtered composition were compared. did. As a result, the blended fragrance composition to which the compound was added had a citrus aroma and a citrus-flavored natural feeling, fresh feeling and fruit juice feeling, and became a fragrance that captured the characteristics of natural lemon. Furthermore, the effect of giving the heavyness of freshly squeezed lemon juice was also recognized, and the point of palatability was also excellent.

Example 5
As a grapefruit-like blended fragrance composition, a basic blended fragrance composition comprising the components shown in Table 3 below was prepared.

  A grapefruit-like blended fragrance composition was prepared by mixing 100 g of the above composition with 0.005 g of 2 (E), 8 (Z) -tetradecadien-1-al produced in Example 1. 1 g of this blended fragrance composition was added to 1000 ml of water, and the filtered composition was compared with 1 g of the above basic blended fragrance composition not containing the compound added to 1000 ml of water, and the aroma and flavor of the filtered composition were compared. . As a result, the blended fragrance composition added with the compound emphasized the natural feeling, freshness, fruit juice and fleshiness of citrus aroma and citrus flavor, and captured the characteristics of natural grapefruit. Furthermore, it is a fragrance peculiar to the above-mentioned basic blended fragrance composition, and has an effect such as suppressing an oily part that gives an artificial impression and adjusting the balance of the fragrance, and is remarkably excellent in terms of palatability.

Example 6
A lemon fragrance composition of the present invention was prepared by mixing 99.99998 g of commercially available lemon essence and 0.00002 g of 2 (E), 8 (Z) -tetradecadien-1-al. A soft drink with the composition shown in Table 4 was prepared using a commercially available lemon essence or lemon fragrance composition.

  The natural feeling, peel feeling and fruit juice feeling of the soft drink B using the commercially available lemon essence and the soft drink B using the lemon flavor composition were compared. As a result, the soft drink B using the lemon fragrance composition was much superior to the soft drink A in the sense of naturalness, peel and fruit juice of lemon.

Example 7
The grapefruit fragrance composition of the present invention was prepared by mixing 99.99997 g of commercially available grapefruit essence and 0.0003 g of 2 (E), 8 (Z) -tetradecadien-1-al. Using a commercially available grapefruit essence or grapefruit fragrance composition, sparkling liquor was prepared with the composition shown in Table 5.

  The natural feeling, freshness, fleshiness and fruit juice feeling of Effervescent Sake A using a commercially available grapefruit essence and Effervescent Sake B using a grapefruit fragrance composition were compared. As a result, effervescent liquor B using the grapefruit fragrance composition was much superior to effervescent liquor A in grapefruit naturalness, freshness, fleshiness and fruit juice.

Example 8
A jelly containing 10% fruit juice was prepared with the composition shown in Table 6.

  Jelly A and Jelly B oranges were compared in terms of naturalness, freshness, and fruit juice. As a result, the jelly B added with 2 (E), 8 (Z) -tetradecadiene-1-al was much superior to the jelly A in the naturalness, freshness, and fruit juice of orange.

The 2 (E), 8 (Z) -tetradecadien-1-al of the present invention exhibits a unique green note, flavedo-like, fruit-like and fat-like aroma, and has a natural and fresh feeling in citrus aroma and flavor. Etc. can be imparted or enhanced. Therefore, it is useful as a fragrance material to be added to food and drink.

Claims (7)

Following formula (1)

2 (E), 8 (Z) -tetradecadiene-1-al represented by   A perfume composition comprising 2 (E), 8 (Z) -tetradecadiene-1-al as an active ingredient.   The fragrance composition according to claim 2, wherein the content of 2 (E), 8 (Z) -tetradecadien-1-al is 5 ppb to 100,000 ppm in the fragrance composition.   The fragrance composition according to claim 2 or 3, further comprising a citrus fragrance component.   Food / beverage products containing the fragrance | flavor composition in any one of Claims 2-4.   2 (E), 8 (Z) -tetradecadien-1-al is added to a fragrance composition, a method for improving citrus aroma. A method for improving citrus flavor, which comprises adding 2 (E), 8 (Z) -tetradecadien-1-al to food and drink.

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