JP5688995B2 - Flavor improver - Google Patents

Description

  The present invention relates to a flavor improving agent, and more specifically,

Wherein ... represents a single bond or a double bond, wavy line indicates the configuration of the cis or trans configuration (although, (E, Z, Z)-2,4,7 tridecanol triethanolamine knurl And (Z, Z) -4,7-tridecadienal)).

  (E, Z, Z) -2,4,7-tridecatrienal is found in the flavor of cooked chicken (Non-patent Document 1), and a thermal decomposition product of arachidonic acid (Non-patent Document 2) or phosphorus. It is a naturally occurring volatile compound that has been found from a pyrolyzate of lipids (Non-patent Document 3) and the like, and is also present in nature. As a fragrance use, a method of imparting a flavor reminiscent of chickens (Patent Document 1), recalling chickens by using 4-cis decenal and (E, Z, Z) -2,4,7-tridecatrienal in combination A method (Patent Document 2) for providing a flavor to be used has been proposed.

  In addition, (E, E, Z) -2,4,7-tridecatrienal and (E, E, E) -2,4,7-tridecatrienal are phospholipid thermal decomposition products (Non-patent Document 3). It is found from.

  The aroma characteristics of these compounds are as follows: (E, Z, Z) -2,4,7-tridecatrienal is Egg white-like, (E, E, Z) -2,4,7-tridecatrienal is Animal, beefy, (E, E, E) -2,4,7-tridecatrienal is described as Animal, pig (Non-patent Document 3).

  In addition, (Z, Z) -4,7-tridecadienal has been reported as a component of exocrine products from the secretory line above the eyes of Oribia (Ourebia ourebi) from natural products (Non-patent Document 4). As a fragrance application, a method of imparting a flavor reminiscent of chicken (Patent Document 1) and a use as a cosmetic fragrance (Patent Document 3) have been proposed. However, in Non-Patent Documents 1 to 4 and Patent Documents 1 to 3, by adding a trace amount of 2,4,7-tridecatrienal or 4,7-tridecadienal to the food or drink, There is no description or suggestion that the taste itself can be improved, that is, the natural taste such as richness, richness, saltiness, and complexity of food and drink can be enhanced. In addition, there is no description or suggestion that adding a trace amount to a food and drink having a fish flavour enhances the woody sensation and knot sensation peculiar to the fish bun and improves the flavor of the fish bun.

Japanese Patent Publication No.41-7822 Japanese Patent Publication No.54-12550 JP-A 61-65814

Journal of American Oil Chemist's Society. 51 (8), 356-9 (1974) Frontiers of Flavor Science, [Proceedings of the Welman Flavor Research Symposium], 9th, Freising, Germany, June 22-25, 1999 (2000). Journal of Agricultural and Food Chemistry (2004), 52 (3), 581-586 Journal of Chemical Ecology (1995), 21 (8), 1191-1215

  The objective of this invention is providing the flavor improving agent of food-drinks. Moreover, it is providing the taste enhancer which can reinforce the deliciousness of food-drinks. Furthermore, the present invention is to provide a fish knot flavor improving agent capable of enhancing the woody taste and knot feeling peculiar to fish knots and improving the fish knot flavor.

  The present applicant has first described (E, Z, Z) -2,4,7-tridecatrienal and (Z, Z) -4,7-tridecadienal as food and drink having fish-flavored flavor. It was found that the addition of a small amount can enhance the feeling of woody and knots peculiar to fish sections and improve the flavor of fish sections (Japanese Patent Application No. 2010-180193). Moreover, the taste of food and drink is obtained by adding a trace amount of (E, Z, Z) -2,4,7-tridecatrienal and (Z, Z) -4,7-tridecadienal to food and drink. A patent application was filed by discovering that it can improve itself, that is, it can enhance the natural taste such as richness, richness, saltiness and complexity of food and drink (Japanese Patent Application No. 2010-247611).

  The applicant then synthesized further geometrical isomers related to the above two compounds of these compounds and evaluated their flavor characteristics. As a result, the geometric isomers related to the above two compounds can also enhance the natural taste such as richness, richness, salty taste, complexity, etc. It was confirmed that by adding a small amount, it was possible to enhance the woody feeling and knot feeling peculiar to the fish section and to improve the flavor of the fish section.

Thus, the present invention provides the following.
(A) The following formula ( 2 )

[In the formula, ... Represents a single bond or a double bond, and a wavy line represents a cis or trans configuration.] (However, (E, Z, Z) -2,4,7-tridecatrie Nar , (E, E, Z) -2,4,7-tridecatrienal, (E, E, E) -2,4,7-tridecatrienal and (Z, Z) -4,7-trideca The flavor improving agent which consists of unsaturated aldehyde represented by (except dienal).
(B) The following formula ( 2 )

［式中、・・・は単結合または二重結合を示し、波線はシスまたはトランス配置の立体配置を示す］（ただし、（Ｅ，Ｚ，Ｚ）−２，４，７−トリデカトリエナール（Ｅ，Ｅ，Ｚ）―２，４，７−トリデカトリエナール、（Ｅ，Ｅ，Ｅ）―２，４，７−トリデカトリエナール、および（Ｚ，Ｚ）−４，７−トリデカジエナールを除く）で表される不飽和アルデヒドからなる飲食品の呈味増強剤を式（１）の不飽和アルデヒドとして１０^−２ｐｐｍ〜１０^４ｐｐｍ含有することを特徴とする飲食品の呈味増強剤組成物。
（ｇ）下記式（１）

［式中、・・・は単結合または二重結合を示し、波線はシスまたはトランス配置の立体配置を示す］（ただし、（Ｅ，Ｚ，Ｚ）−２，４，７−トリデカトリエナールおよび（Ｚ，Ｚ）−４，７−トリデカジエナールを除く）で表される不飽和アルデヒドからなる飲食品の呈味増強剤を、式（１）の不飽和アルデヒドとして１０^−３ｐｐｂ〜１０^４ｐｐｂ添加することを特徴とする飲食品の呈味増強方法。
（ｈ）（ｆ）の飲食品の呈味増強剤組成物を、式（１）の不飽和アルデヒドとして１０^−３ｐｐｂ〜１０^４ｐｐｂ添加することを特徴とする飲食品の呈味増強方法。
（ｉ）下記式（３）

[In the formula,... Represents a single bond or a double bond, and a wavy line represents a cis or trans configuration.] (However, (E, Z, Z) -2,4,7-tridecatrienal, (E, E, Z) -2,4,7-tridecatrienal, (E, E, E) -2,4,7-tridecatrienal and (Z, Z) -4,7-tridecadienal The taste enhancer of the food-drinks which consist of unsaturated aldehyde represented.
(C) The food / beverage taste enhancer according to (b), wherein the food / beverage product is a food / beverage product having a delicious taste.
(D) The taste enhancer for food or beverage according to (b) or (c), wherein the taste enhancement is enhancement of umami.
(E) The food or drink having a delicious taste is a food or drink containing one or more selected from amino acids, nucleic acids, organic acids, oils and fats, and salt (b) to (d) A taste enhancer for food or drink according to any one of the above.
(F) The following formula (1)

[In the formula,... Represents a single bond or a double bond, and a wavy line represents a cis or trans configuration.] (However, (E, Z, Z) -2,4,7-tridecatrienal ( E, E, Z) -2,4,7-tridecatrienal, (E, E, E) -2,4,7-tridecatrienal, and (Z, Z) -4,7-tridecadienal the excluded) in taste enhancement of food or drink, characterized by containing ¹⁰ -2 ppm~10 4 ^ppm a food or beverage taste enhancer consisting of an unsaturated aldehyde as unsaturated aldehydes of the formula (1) represented Agent composition.
(G) The following formula (1)

[In the formula,... Represents a single bond or a double bond, and a wavy line represents a cis or trans configuration.] (However, (E, Z, Z) -2,4,7-tridecatrienal and 10 ⁻³ ppb to 10 ppb to 10 ppb as the unsaturated aldehyde of the formula (1) is used as a food / beverage product taste enhancer comprising an unsaturated aldehyde represented by (Z, Z) -4,7-tridecadienal). ⁴ ppb addition, The taste enhancement method of the food-drinks characterized by the above-mentioned.
(H) A method for enhancing the taste of a food or drink, comprising adding 10 ⁻³ ppb to 10 ⁴ ppb of the flavor enhancer composition of the food or drink of (f) as an unsaturated aldehyde of the formula (1).
(I) The following formula (3)

[In the formula, ... Represents a single bond or a double bond, and a wavy line represents a cis or trans configuration.] (However, (E, Z, Z) -2,4,7-tridecatrie Noodles , except for (E, E, Z) -2,4,7-tridecatrienal and (Z , Z) -4,7-tridecadienal ) Agent.
(J) A fish fragrance composition containing 10 ⁻² ppm to 10 ⁴ ppm of the unsaturated aldehyde concentration of formula (1) of the fish flavour improvement agent according to (i).
(K) A food / beverage product containing the fish fragrance composition according to (j) in an amount of 10 ⁻³ ppb to 10 ⁴ ppb as the unsaturated aldehyde concentration of formula (1).

  There are reports that (E, E, Z) -2,4,7-tridecatrienal and (E, E, E) -2,4,7-tridecatrienal used in the present invention were found from natural products. Yes (Non-Patent Document 3), and (E, E, Z) -2,4,7-tridecatrienal has been proposed for use as a chicken-like flavor (Patent Document 1). Reference 1 does not describe an example in which (E, E, Z) -2,4,7-tridecatrienal is actually used as a fragrance. (E, Z, E) -2,4,7-tridecatrienal, (E, Z) -4,7-tridecadienal, (Z, E) -4,7-tridecadienal and Regarding (E, E) -4,7-tridecadienal, no description is found in the prior literature.

  Therefore, these compounds have not yet been reported as taste enhancers, and moreover, the content of enhancing the umami taste such as richness, richness, salty taste and complexity by adding to foods and drinks It has never been described or suggested. In addition, these compounds have not yet been reported as components of fish sections, and there is no description that they are used as fish section flavors.

The unsaturated aldehyde which is an active ingredient of the flavor improving agent of the present invention is a food / beverage product, in particular, a food / beverage product having a delicious taste, as well as an amino acid, a nucleic acid, an organic acid, an oil / fat, a salt, and the like as a taste enhancer. By adding 10 ⁻³ ppb to 10 ⁴ ppb to the food or drink to be contained, it is possible to enhance a natural umami taste that has not existed before. Further, as the taste enhancer composition, the composition contains 10 ⁻² ppm to 10 ⁴ ppm of an unsaturated aldehyde which is an active ingredient of the taste enhancer of the present invention, and the taste enhancer composition is eaten or consumed. The same effect can be obtained by adding to the product.

Moreover, the unsaturated aldehyde which is an active ingredient of the flavor improving agent of this invention mix | blends 10 ^<-2 > ppm-10 ^{< 4} > ppm in the fish fragrance | flavor composition which has a fish ^- bush-like fragrance | flavor, especially a bonito-like fragrance as a fish ^- blossom flavor improving agent. By doing so, it is possible to give a woody feeling and knot feeling peculiar to fish buns, which is not found in the past. Moreover, by adding the fish fragrance composition to the food or drink product as an unsaturated aldehyde so as to be 10 ⁻³ ppb to 10 ⁴ ppb, it is possible to impart a fish-like woody feeling and a taste with a knotty feeling. .

FIG. 1 is a gas chromatography chart of (E, E, Z) -2,4,7-tridecatrienal. (Example 1) FIG. 2 is a ¹ H-NMR chart of (E, E, Z) -2,4,7-tridecatrienal. Example 1 FIG. 2 is a ¹³ C-NMR chart of (E, E, Z) -2,4,7-tridecatrienal. Example 1 FIG. 4 is a gas chromatography chart of (E, Z, E) -2,4,7-tridecatrienal. (Example 2) FIG. 5 is a ¹ H-NMR chart of (E, Z, E) -2,4,7-tridecatrienal. (Example 2) FIG. 6 is a ¹³ C-NMR chart of (E, Z, E) -2,4,7-tridecatrienal. (Example 2) FIG. 7 is a gas chromatography chart of (E, E, E) -2,4,7-tridecatrienal. (Example 3) FIG. 8 is a ¹ H-NMR chart of (E, E, E) -2,4,7-tridecatrienal. (Example 3) FIG. 9 is a ¹³ C-NMR chart of (E, E, E) -2,4,7-tridecatrienal. (Example 3) FIG. 10 is a gas chromatography chart of (E, Z) -4,7-tridecadienal. Example 4 FIG. 11 is a ¹ H-NMR chart of (E, Z) -4,7-tridecatrienal. Example 4 FIG. 12 is a ¹³ C-NMR chart of (E, Z) -4,7-tridecatrienal. Example 4 FIG. 13 is a gas chromatography chart of (Z, E) -4,7-tridecadienal. (Example 5) FIG. 14 is a ¹ H-NMR chart of (Z, E) -4,7-tridecatrienal. (Example 5) FIG. 15 is a ¹³ C-NMR chart of (Z, E) -4,7-tridecatrienal. (Example 5) FIG. 16 is a gas chromatography chart of (E, E) -4,7-tridecadienal. (Example 6) FIG. 17 is a ¹ H-NMR chart of (E, E) -4,7-tridecatrienal. (Example 6) FIG. 18 is a ¹³ C-NMR chart of (E, E) -4,7-tridecatrienal. (Example 6)

  The unsaturated aldehyde used in the present invention is specifically (E, E, Z) -2,4,7-tridecatrienal, (E, Z, E) -2,4,7-tridecatrie. Nar, (E, E, E) -2,4,7-tridecatrienal, (E, Z) -4,7-tridecadienal, (Z, E) -4,7-tridecadienal and (E, E) -4,7-tridecadienal.

  These compounds used in the present invention can be synthesized by, for example, the following method.

  (E, E, Z) -2,4,7-tridecatrienal, for example, performs Horner-Wards-Emmons reaction using commercially available cis-3-nonenal as a starting material (E, E, Z) -2, 4,7-tridecatrienol ester is subjected to diisobutylaluminum hydride (DIBAL) reduction without purification, and the obtained (E, E, Z) -2,4,7-tridecatrienol is purified by a known purification method. Can be obtained by oxidation after purification.

  In addition, (E, Z, E) -2,4,7-tridecatrienal is, for example, brominated commercially available (E) -oct-2-en-1-ol, and the resulting bromide and 2-propyne Coupling of -1-ol in the presence of a copper reagent gives (E) -undec-5-en-2-yn-1-ol, and then the Wittig reaction after the triple bond is converted to a double bond by Lindlar reduction. To (E, Z, E) -2,4,7-tridecatriene ester, which can be obtained through reduction and oxidation.

  In addition, (E, E, E) -2,4,7-tridecatrienal is obtained by, for example, obtaining (E) -undec-5-en-2-yn-1-ol by the same method as described above. The lithium dihydride (LAH) is reduced, and the resulting diene alcohol is led to (E, E, E) -2,4,7-tridecatriene ester by the oxidation Wittig reaction, and obtained through reduction and oxidation. it can.

  In addition, (E, Z) -4,7-tridecadienal is, for example, coupled with pentyl bromide with 2-propyn-1-ol to form 2-octyn-1-ol, then brominated, After 2-propyn-1-ol was coupled to give 2,5-undecadin-1-ol, lithium aluminum hydride (LAH) reduction was performed to obtain (E) -2 alcohol, which was left behind. (E, Z) -2,5-diene alcohol is obtained by converting the triple bond into a double bond by Lindlar reduction, and then the carbon chain is extended through malonic ester condensation and decarbonylation, and the resulting diene alcohol is obtained. It can be obtained by oxidizing.

  In addition, (Z, E) -4,7-tridecadienal, for example, brominates commercially available (E) -2-octyn-1-ol and then 4-pentyne-1-in the presence of a copper reagent. It is possible to obtain (E) -tridec-7-en-4-yn-1-ol by coupling allol, and then oxidize after converting the triple bond to a double bond by Lindlar reduction.

  In addition, (E, E) -4,7-tridecadienal is obtained, for example, by the same method as above to obtain (E) -tridec-7-en-4-yn-1-ol, which is reduced by birch. Then, after obtaining the diene alcohol, it can be obtained by oxidizing the hydroxyl group.

  Each of the unsaturated aldehydes of the present invention may be used alone, but the effect as a flavor improving agent can be further enhanced by using a combination of plural unsaturated aldehydes in combination. At this time, (E, Z, Z) -2,4,7-tridecatrienal or (Z, Z) -4,7-tridecadienal may be used in combination. Arbitrary ratios can be mentioned as the compounding ratio in the combined use.

  In this invention, the flavor of food-drinks can be improved by adding these unsaturated aldehydes to food-drinks in trace amount, and it can be used as a flavor improving agent.

  As one aspect of the flavor improvement in the present invention, an increase in the taste of food and drink can be exemplified. Therefore, the unsaturated aldehyde of the present invention can be used as a taste enhancer for food and drink. A food or drink whose taste is enhanced by the addition of the taste enhancer of the present invention is a food or drink having a delicious taste, and the enhanced taste is mainly the taste of a food or drink.

  The umami taste referred to in the present invention is a taste reminiscent of richness, richness, saltiness, complexity, etc., which is a taste that is felt on the tongue rather than mainly as an aroma, and also has a natural material. It means a sense of taste reminiscent of a natural atmosphere.

  Foods and drinks having a umami taste are foods and drinks that are relatively rich in amino acids, nucleic acids, organic acids, oils and fats, salt, etc., and these amino acids, nucleic acids, organic acids, oils and fats, salt, etc. Either a natural product or a synthetic product may be used.

  Such foods and beverages include, for example, rice crackers, hail, rice cakes, potatoes, buns, sea urchins, bean jam, water sheep kan, brocade, jelly, castella, jasper, biscuits, crackers, potato chips, cookies, Pastries such as pie, pudding, butter cream, custard cream, cream puff, waffle, sponge cake, donut, chocolate, chewing gum, caramel, candy, peanut paste, etc .; bread, udon, ramen, Chinese noodles, sushi, Gomoku rice, fried rice, pilaf, gyoza skin, shumai skin, okonomiyaki, takoyaki, and other breads, noodles, rice; pickles, pickled plums, Fukujin pickles, pickled pickles, pickled pickles, pickles, miso pickles, pickled pickles, Pickles such as those pickles; mackerel, Fishes such as eagle, saury, salmon, tuna, skipjack, whale, flounder, squidfish, sweetfish, squid, squid, coat squid, firefly squid, octopus such as octopus, squid, lobster, button shrimp, lobster, lobster, Shrimp such as black tiger, sea crabs such as king crab, snow crab, crabs and crabs, clams such as clams, clams, scallops, oysters, mussels; canned, boiled fish, boiled fish, surimi, marine products (chikuwa Processed food and drinks of seafood such as fried, tempura, etc .; livestock such as chicken, pork, beef, lamb, horse meat; curry, stew, beef stew, coconut rice sauce, Such as meat sauce, mabo tofu, hamburger, dumplings, pot rice, soup, meat dumplings, simmered meat, canned meat Processed foods and drinks using meat; table salt, seasoning salt, soy sauce, powdered soy sauce, miso, powdered miso, moromi, hashio, sprinkle, tea sauce, margarine, mayonnaise, dressing, vinegar, three cups vinegar, powdered sushi vinegar, Chinese Nomoto, Tentsuyu, Noodle soup, Sauce, Ketchup, Grilled meat sauce, Carrero, Stew, Stew, Soup, Dashimoto, Compound seasoning, Shin mirin, Fried / Takoyaki mixed powder, etc. Seasonings, etc .; dairy products such as cheese and butter, boiled vegetables, boiled dishes such as Chikuzen boiled rice, oden and pots, take-out lunch boxes, side dishes, tomato juice, sports drinks and the like.

  Among these foods and beverages, the taste enhancer of the present invention is a food that has a reduced fat content in order to reduce calories; a low-salt food in which salt is reduced to reduce sodium intake; Amino acid seasonings such as sodium glutamate, aspartic acid, arginine and serine, nucleic acid seasonings such as guanylic acid, adenylic acid and inosinic acid, organic acid seasonings such as succinic acid, It is particularly effective for foods and drinks that contain a lot of seasonings.

  The unsaturated aldehyde of the present invention can be used as a taste enhancer as it is added to food and drink as it is, but the unsaturated aldehyde of the present invention is oil-soluble, as it is, its dispersibility in water is poor, Since it is difficult to add trace amounts to foods and drinks from the viewpoint of weighing and dilution, a method of blending a trace enhancer composition of the present invention to obtain a taste enhancer composition and blending it into foods and drinks Can be adopted. Examples of such a composition include a solution obtained by dissolving the unsaturated aldehyde of the present invention in a water-miscible organic solvent, an emulsion preparation, and a powder preparation.

  Examples of the water-miscible organic solvent for dissolving the unsaturated aldehyde of the present invention include ethanol, methanol, acetone, tetrahydrofuran, acetonitrile, 2-propanol, methyl ethyl ketone, glycerin, propylene glycol and the like. Among these, ethanol or glycerin is particularly preferable from the viewpoint of use in foods and drinks.

  Moreover, in order to set it as an emulsion formulation, it can obtain by emulsifying the unsaturated aldehyde of this invention with an emulsifier. The method for emulsifying the unsaturated aldehyde of the present invention is not particularly limited, and various emulsifiers conventionally used in foods and drinks, such as fatty acid monoglyceride, fatty acid diglyceride, fatty acid triglyceride, propylene glycol fatty acid ester, Using sugar fatty acid ester, polyglycerin fatty acid ester, lecithin, modified starch, sorbitan fatty acid ester, quilaya extract, gum arabic, tragacanth gum, guar gum, caraya gum, xanthan gum, pectin, alginic acid and its salts, carrageenan, gelatin, casein, etc. An emulsified liquid having excellent stability can be obtained by emulsifying using a homomixer, a colloid mill, a rotating disk type homogenizer, a high-pressure homogenizer, or the like. The amount of these emulsifiers to be used is not strictly limited, and can be varied over a wide range depending on the type of emulsifier to be used. Usually, about 0. A suitable range is 01 to about 100 parts by weight, preferably about 0.1 to about 50 parts by weight. In order to stabilize the emulsification, the water-soluble solution is one of polyhydric alcohols such as glycerin, propylene glycol, sorbitol, maltitol, sucrose, glucose, trehalose, sugar solution, and reduced water candy. A seed or a mixture of two or more can be blended.

  Further, the emulsion thus obtained can be made into a powder formulation by drying if desired. In pulverization, saccharides such as trehalose, dextrin, sugar, lactose, glucose, starch syrup, and reduced starch syrup can be appropriately blended as necessary. The amount of these used can be appropriately selected according to the properties desired for the powder preparation.

  In addition, in the composition containing the unsaturated aldehyde that is an active ingredient of the taste enhancer of the present invention, arbitrary components can be combined, and various flavoring ingredients, oil-soluble pigments, vitamins, functionality Examples include substances, fish meat extracts, animal meat extracts, vegetable extracts, yeast extracts, animal and plant proteins, animal and plant protein degradation products, starch, dextrin, saccharides, amino acids, nucleic acids, organic acids, solvents, etc. it can.

The amount of addition of the unsaturated aldehyde of the present invention to the taste enhancer composition of the present invention is not particularly limited, but the amount of addition of the taste enhancer composition to food or drink is usually about 0.01% to Since it is about 1%, the blending amount of the unsaturated aldehyde of the present invention to the taste enhancer composition is 10 ⁻² ppm to 10 ⁴ ppm, preferably 0.1 ppm to 10 ³ ppm, more preferably 1 ppm. ~ 100 ppm.

In this invention, the addition amount of the unsaturated aldehyde of this invention to food / beverage products is important, and as mentioned above, the taste of food / beverage products is enhanced by adding to food / beverage products in a specific concentration range. In this case, the amount of the unsaturated aldehyde of the present invention added to the food or drink is 10 ⁻³ ppb to 10 ⁴ ppb, preferably 10 ⁻² ppb to 10 ³ ppb, more preferably 0 as the unsaturated aldehyde of the present invention. .1 ppb to 100 ppb. When the amount added to the food or drink is less than 10 ⁻³ ppb, the taste enhancing effect that is the effect of the present invention cannot be obtained, and when the amount added to the food or drink exceeds 10 ⁴ ppb, An aldehyde-like aroma unique to unsaturated aldehydes can be felt. Therefore, it is generally used at an addition amount of less than 10 ⁴ ppb, but when the aroma of the unsaturated aldehyde itself of the present invention is not a problem, it may be used at an amount exceeding 10 ⁴ ppb.

  Further, as another aspect of flavor improvement in the present invention, fish flavor improvement can be particularly exemplified. The unsaturated aldehyde of the present invention is usually used in foods and drinks having a fish-flavored flavor such as bonito, Soda, mackerel, sardine, muro, saury, namari, tuna, and boiled, rather than being used as a fragrance. By adding to a food or drink in a small amount, the fish flavor can be improved. Therefore, the unsaturated aldehyde of the present invention can be used as a fish clause flavor improving agent. In addition, the unsaturated aldehyde of the present invention is blended in a trace amount in a fragrance composition having a fish bonito flavor such as bonito, soda, mackerel, sardine, muro, saury, namari, tuna, and boiled and dried. Thus, by obtaining a fragrance composition and blending it into a food or drink or seasoning, it is possible to impart a woody and unsavory flavor unique to fish knots that has never been known before.

  Examples of the material for the fish fragrance composition include bonito extract, soda set extract, mackerel set extract, sardine set extract, muro set extract, saury set extract, namari set extract, tuna set extract, and boiled extract. Extracts: Yeast extracts obtained from yeasts such as beer yeast, baker's yeast, torula yeast, etc. by methods such as self-digestion, enzymatic degradation, acid degradation; soy, wheat, corn, gelatin, whey protein, fish meal, casein Animal and plant proteolysates obtained by chemically or enzymatically degrading proteins such as egg white, bone extract, etc .; fractionation means selected from extraction and / or distillation and / or adsorption treatment from fish or fishfish extract And a fragrance component. Examples of the fragrances include hydrocarbons such as limonene, cyclopentene, methylbenzene, and δ-casinene; isoamyl alcohol, 1-penten-3-ol, 1-octen-3-ol, (Z, Z)- 1,5,8-undecatrien-3-ol, 2-phenylethanol, 2,5-octadien-3-ol, (Z)-or (E) -2-penten-1-ol, (Z)- 2-penten-3-ol, (E) -2-hexen-1-ol, (E) -2-octen-1-ol, (Z)-or (E) -1,5-octadien-3-ol , (Z) -1,5-undecadien-3-ol; propanal, butanal, pentanal, (E) -2-pentenal, hexanal, (Z) -3-hexenal, (E -2-hexenal, heptanal, (E) -2-heptenal, (Z) -4-heptenal, 2,4-heptadienal, (E, Z) or (E, E) -2,4-heptadienal, octanal, ( Z) or (E) -2-octenal, (E, E) -2,4-octadienal, (E, Z) -2,5-octadienal, nonanal, (E) -2-nonenal, ( E, Z) -2,6-nonadienal, decanal, 2,4-decadienal, (E, Z) or (E, E) -2,4-decadienal, (E) -2-undecenal, benzaldehyde, cuminaldehyde, Aldehydes such as phenylacetaldehyde, cinnamaldehyde, 2-phenyl-2-butenal; 2-butanone, acetoin, diacetyl, 3-pentene-2 -One, 3-hydroxy-2-pentanone, 2,3-pentanedione, 3-hexanone, 2-heptanone, 6-methyl-5-hepten-2-one, 2-octanone, 3-octanone, (E, Z ) Or (E, E) -3,5-octadien-2-one, 2-nonanone, 2-decanone, 2-undecanone, (E) -6,10-dimethyl-5,9-undecadien-2-one, Cyclopentanone, 2-cyclopenten-1-one, 2- or 3-methylcyclopentanone, 2,3,4 or 5-methyl-2-cyclopenten-1-one, 2,3-dimethyl-2-cyclopentene- 1-one, 2,4-, 2,5-, 3,4- or 3,5-dimethyl-2-cyclopenten-1-one, 2,3,4-trimethyl-2-cyclopenten-1-one, Ketones such as danone, cycloten, cyclohexanone, 2-cyclohexen-1-one, 2- or 3-methyl-2-cyclohexen-1-one, acetophenone, propiophenone, camphor; acetic acid, propionic acid, 2-methylpropion Acids such as lactic acid, butyric acid, 2-methylbutyric acid, isovaleric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, benzoic acid and phenylacetic acid; ethyl formate, ethyl acetate, methyl benzoate, 2-methylbenzoic acid Esters such as methyl acid and methyl 4-methylbenzoate; Lactones such as butyrolactone, 4-hydroxy-3-methylbutanoic acid lactone and γ-valerolactone; Trimethylamine, 1,4-butanediamine, 1,5-butanediamine , Phenylethylamine, 2- (4-hydroxypheny ) -1,4-butanediamine, pyrrole, 2-acetylpyrrole, indole, 2-methylindole, 3-methylindole, pyridine, 2,3 or 4-methylpyridine, 2 or 3-ethylpyridine, 3-vinyl Pyridine, 3-methoxypyridine, quinoline, pyrazine, methylpyrazine, ethylpyrazine, 2,3-, 2,5- or 2,6-dimethylpyrazine, 2-ethyl-5- or 6-methylpyrazine, trimethylpyrazine, 3 -Nitrogenous bases such as ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, tetramethylpyrazine, 2-ethyl-3,5-dimethoxypyrazine; methanethiol, dimethylsulfide, dimethyldisulfide , Carbon disulfide, methional, thiazole, 2 Sulfur-containing compounds such as 4-dimethylthiazole and 2,4,5-trimethylthiazole; ethers such as 1,8-cineol and 1,4-cineole; acetonitrile, 3-methylbutanenitrile, 4-methylpentanenitrile, Nitriles such as benzonitrile and phenylacetonitrile; o-, m- or p-cresol, 2-ethylphenol, 4-vinylphenol, 2-isopropylphenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenol, 2-ethyl-5-methylphenol, 5-ethyl-3-methylphenol, 2,3,5- or 2,4,6-trimethylphenol, 1-methoxy-3-methylbenzene, 1-methoxy-4-propylbenzene, 2-methoxy-4-methyl Enol, 4-ethyl-2-methoxyphenol, 2-methoxy-4-propylphenol, eugenol, isoeugenol, 1,2-dimethoxybenzene, 1,2-dimethoxy-4-methylbenzene, 1,3-dimethoxy-5 Methylbenzene, 4-ethyl-1,2-dimethoxybenzene, 1,2-dimethoxy-4-propylbenzene, methyleugenol, methylisoeugenol, (Z) or (E) 1,2-dimethoxy-4- (1 -Propenyl) benzene, safrole, isosafrole, 1,2,3- or 1,3,5-trimethoxybenzene, 2,6-dimethoxyphenol, 2,6-dimethoxy-4-methylphenol, 4-ethyl-2 , 6-dimethoxyphenol, 2,6-dimethoxy-4-propylphenol, 1,2 , 3-trimethoxy-5-methylbenzene, 5-ethyl-1,2,3-trimethoxybenzene, 1,2,3-trimethoxy-5-vinylbenzene, 1,2,3-trimethoxy-5-propylbenzene, Aromatic compounds such as 1,2,3-trimethoxy-5- (1-propenyl) -benzene, guaiacol, 4-methylguaiacol, 4-ethylguaiacol; 2-methylfuran, 2-ethylfuran, 2-pentylfuran , (Z) -2- (2-pentenyl) furan, 2-hexyl-5-methylfuran, 2-ethyl-5-vinylfuran, benzofuran, 2-methylbenzofuran, 2-ethylbenzofuran, furfural, 2-methyl- Dihydro-3 (2H) -furanone, 3-methyl-2 (5H) -furanone, 3,4-dimethyl-2 (5H) -furan 3,4,5-trimethyl-2 (3H) -furanone, 3,4,5-trimethyl-2 (5H) -furanone, 5-ethyl-3,4-dimethyl-2 (5H) -furanone, 3, , 4-Dimethyl-5-propyl-2 (5H) -furanone, 3,4-Dimethyl-5-pentyl-2 (5H) -furanone, 2-acetylfuran, 2-acetyl-5-methylfuran, furfuryl alcohol , Furan and pyran such as 2-furancarboxylic acid, 5-methyl-2-furancarboxylic acid, methyl 2-furancarboxylate, furfuryl acetate, maltol, 2,3-dimethylbenzopyran, etc. The fish-flavored fragrance | flavor composition which mixed combining these arbitrarily can be mention | raise | lifted.

The blending amount of the unsaturated aldehyde of the present invention as a fish fragrance improving agent is also important and varies depending on the purpose or the type of the fish fragrance composition. 10 ⁻² ppm to 10 ⁴ ppm, preferably 0.1 ppm to 1000 ppm, more preferably 1 ppm to 100 ppm. Within these ranges, it has an excellent effect of imparting a woody feeling, a knot feeling, and the like peculiar to fish sections to the fish set flavor composition.

  Here, woody feeling and knot feeling are preferable aromas unique to fish sections such as bonito, and fresh fragrance that makes you imagine the freshly-cut fragrance that occurs when you cut bonito, etc. It means a refreshing fragrance that reminds you of the fragrance.

On the other hand, when the blended amount of the unsaturated aldehyde of the present invention with respect to the fish fragrance composition exceeds 10 ⁴ ppm, the aroma and flavor characteristics appear as citrus-like, soap-like, and degraded oil-like odors. It is not preferable. Moreover, when the compounding quantity of the unsaturated aldehyde of this invention with respect to a fish fragrance | flavor composition is less than 10 ^<-3 > ppm, the fragrance and flavor imparting effect peculiar to this invention are not acquired.

  Furthermore, the present invention relates to a food or drink characterized by adding an effective amount of a fish set flavor composition containing a fish set flavor improving agent containing the unsaturated aldehyde of the present invention as an active ingredient. It is possible to give a scent and flavor with a woody feeling and modest feeling. Such foods and drinks only need to contain at least part of the fish set flavor and can be used in various foods and drinks in a wide range of fields.

  Examples of these foods and beverages include amino acid seasonings, nucleic acid seasonings, sour seasonings, fermented seasonings, pork extract, chicken extract, seafood extract, yeast extract, protein hydrolysate, soy sauce, miso, vinegar, Three cups of vinegar, powdered sushi vinegar, dressing, mayonnaise, sauce, ketchup, fish sauce, bean plate sauce, fish paste, kelp soup stock, soup stock, Chinese soup, tempura soup, noodle soup, grilled meat sauce, curry roux, stew sauce, soup Moisture, dashi-no-mochi, compound seasonings, seasonings such as mirin, hon mirin, new mirin, soups such as consomme soup, potage soup, ramen soup, soups such as miso soup, soup, pork soup, demiglace sauce for retort food , White sauce, tomato sauce, meat sauce and other sauces, curry, stew, coconut, oden Can.

Further, the amount of the unsaturated aldehyde of the present invention to be added to the food or drink varies depending on the purpose or the type of the food or drink, but the fish set flavor improving agent or the fish set flavor improving composition containing the fish set flavor improving agent is mixed. By adding an effective amount of as an unsaturated aldehyde, a fish knot-like woody feeling and a knotty flavor can be imparted. The compounding quantity to the seasoning or food / beverage products in that case is 10 ^{< -3} > ppb-10 < ⁴ > ppb with respect to the whole mass of food / beverage products as an unsaturated aldehyde of this invention, Preferably, 10 ^<-2 > ppb-10 ^{< 3} >. A range of ppb, more preferably 0.1 ppb to 100 ppb can be exemplified. On the other hand, when the blending amount of the unsaturated aldehyde of the present invention exceeds 10 ⁴ ppb with respect to the total mass of the food or drink, the odor and flavor characteristics as a citrus-like, soap-like, and deteriorated oil-like odor appear. It is not preferable. Moreover, when the compounding quantity of the unsaturated aldehyde of this invention with respect to food-drinks is less than 10 < ^-3 > ppb, the fragrance and flavor imparting effect peculiar to this invention are not acquired.

  Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to Examples, Comparative Examples, and Reference Examples, but the present invention is not limited thereto.

Example 1 Preparation of (E, E, Z) -2,4,7-tridecatrienal (E, E, Z) -2,4,7- of formula (2) according to the following series of reaction formulas Tridecatrienal was synthesized. The percentage in parentheses below the process number indicates the yield of each process.

Ethyl (E, E, Z) -2,4,7-tridecatrienoate (8)
A separately prepared Wittig reagent (7.5 g, 30 mmol) and tetrahydrofuran (THF) (75 ml) were charged into a 200 ml flask, cooled to −78 ° C. and stirred. Sodium bis (trimethylsilyl) amide (NaHMDS) / tetrahydrofuran (1.0 M, 22 ml, 22 mmol) was added dropwise to the system, and the mixture was heated to 22 ° C. and stirred for 30 minutes. The mixture was cooled again to −78 ° C., a solution of (Z) -3-nonenal (7) (2.8 g, 20 mmol) in tetrahydrofuran (20 ml) was added dropwise to the system, and the mixture was stirred for 6 hours. When the reaction was monitored by thin layer chromatography, the temperature was raised to 15 ° C. over 1 hour because the raw material remained. After confirming disappearance of the raw material by thin layer chromatography, a saturated aqueous ammonium chloride solution was added. After separation operation, the aqueous layer was extracted with diethyl ether, combined with the previous organic layer, washed with saturated brine, and then dried over anhydrous magnesium sulfate. After filtration under reduced pressure, the residue obtained by concentration under reduced pressure was purified by silica gel chromatography (100 g, hexane: ethyl acetate = 50: 1), and ethyl (E, E, Z) -2,4,7-tridecatrieno Eight (8) (1.84 g, 39%, purity 50%) was obtained.

(E, E, Z) -2,4,7-tridecatrien-1-ol (9)
A 100 ml two-necked flask was charged with ethyl (E, E, Z) -2,4,7-tridecatrienoate (8) (assuming 50% purity, 500 mg, 2.12 mmol), diethyl ether (30 ml), and a dry ice bath. Was cooled and stirred. Diisobutylaluminum hydride (DIBAL) (solvent: toluene, 0.99M, 4.28 ml, 4.24 mmol) was added dropwise into the system, and the mixture was stirred overnight while gradually raising the temperature. Next, a 10% Rochelle salt aqueous solution was added to the system and stirred at room temperature for 3.0 hours. The aqueous layer was extracted with diethyl ether, and the obtained organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration under reduced pressure, the residue obtained by concentrating the filtrate under reduced pressure was purified by silica gel chromatography (100 g, hexane: ethyl acetate = 10: 1 to 3: 1), and (E, E, Z) -2, 4 , 7-tridecatrien-1-ol (9) (287 mg, 82% yield) was obtained.

(E, E, Z) -2,4,7-Tridecatrienal (2)
A 50 ml eggplant flask was charged with (E, E, Z) -2,4,7-tridecatrien-1-ol (9) (50 mg, 0.26 mmol) and methylene chloride (5 ml) and stirred at room temperature for manganese dioxide (226 mg, 2.6 mmol) was added and stirred for 2 days. After filtration under reduced pressure, the residue obtained by concentrating the filtrate under reduced pressure was purified by silica gel chromatography (10 g, hexane: ethyl acetate = 20: 1) to obtain (E, E, Z) -2,4,7-tride. Cattrienal (2) (36 mg, 72% yield) was obtained.

(Example 2) Preparation of (E, Z, E) -2,4,7-tridecatrienal (E, Z, E) -2,4,7- in formula (3) according to the following reaction formula Tridecatrienal was synthesized. The percentage in parentheses below the process number indicates the yield of each process.

(E) -1-Bromooct-2-ene (11)
(E) -Oct-2-en-1-ol (10) (50 g, 390 mmol), diethyl ether (480 ml) and pyridine (1.4 g) were charged into a 1 L eggplant flask and stirred at room temperature. Phosphorus tribromide (39.2 g, 145 mmol) was added dropwise to the system over 1.0 hour, and the mixture was stirred overnight at room temperature. After confirming disappearance of the raw materials by gas chromatography, a saturated aqueous sodium hydrogen carbonate solution was added to the system and stirred for 30 minutes. The aqueous layer was extracted with diethyl ether, and the obtained organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. After filtration under reduced pressure, the filtrate (E) -1-bromooct-2-ene (11) crude product (58 g) obtained by concentration under reduced pressure was used in the next reaction without further purification.

(E) -Undec-5-en-2-yn-1-ol (12)
A 1 L 4-neck flask was charged with ethyl magnesium bromide / tetrahydrofuran (0.9M, 400 ml, 360 mmol), and stirred under cooling in an ice bath under a nitrogen atmosphere. A solution of 2-propyn-1-ol (9.59 g, 171 mmol) in tetrahydrofuran (130 ml) was added dropwise, stirred at room temperature for 1.5 hours, and then cooled again using an ice bath. Copper cyanide (4.52 g) was added to the system, and after stirring for 15 minutes, a solution of (E) -1-bromooct-2-ene (11) (32.7 g, crude product) tetrahydrofuran (65 ml) was added dropwise. After removing the ice bath and stirring at reflux for 2.0 hours, a saturated aqueous ammonium chloride solution was added to the system. After the separation operation, the aqueous layer was extracted with ethyl acetate, washed with water, a saturated aqueous ammonium chloride solution and a saturated saline solution together with the previous organic layer, and dried over anhydrous magnesium sulfate. After filtration under reduced pressure, (14 g) of the residue (28.6 g) obtained by concentrating the filtrate under reduced pressure was used as a raw material for lithium aluminum hydride (LAH) reduction in Example 3 without further purification. The remaining residue (14 g) was purified by silica gel chromatography (750 g, hexane: ethyl acetate = 30: 1) to give pure (E) -undec-5-en-2-yn-1-ol (12) ( 9.99 g, 70%, 2 steps).

(Z, E) -2,5-Undecadien-1-ol (13)
In a 500 ml three-necked flask, (E) -undec-5-en-2-yn-1-ol (12) (4.0 g, 24.1 mmol), quinoline (400 mg) and Lindlar catalyst (manufactured by N.E. Chemcat) (400 mg) was charged and stirred at room temperature under a hydrogen atmosphere for 5.0 hours. After confirming the disappearance of the raw materials by gas chromatography, the mixture was filtered under reduced pressure, and the filtrate was washed successively with 2N aqueous hydrochloric acid, saturated aqueous bicarbonate, and saturated brine, and dried over anhydrous magnesium sulfate. After filtration under reduced pressure, the filtrate was concentrated under reduced pressure, and the resulting residue (4.0 g) was purified by silica gel chromatography (400 g, hexane: ethyl acetate = 10: 1) to give (Z, E) -2,5- Undecadien-1-ol (13) (3.6 g, 89%) was obtained.

Ethyl (E, Z, E) -2,4,7-tridecatrienoate (14)
(Z, E) -2,5-Undecadien-1-ol (13) (2.11 g, 12.5 mmol) and methylene chloride (150 ml) were added to a 500 ml eggplant flask and stirred. Ethyl (triphenylphosphoranylidene) acetate (28.4 g, 81.5 mmol) was added to the system, and after confirming dissolution, manganese dioxide (21.7 g, 250 mmol) was added. After stirring at room temperature for 120 hours, silica gel (100 g) was added to the filtrate obtained by confirming the disappearance of the raw materials and filtration under reduced pressure, followed by concentration under reduced pressure. Purification by silica gel chromatography (200 g, hexane: ethyl acetate = 20: 1) using silica gel adsorbing the crude product obtained as a residue, and ethyl (E, Z, E) -2,4,7-tride Catrienoate (14) Crude product (2.4 g) was obtained. This crude product was used in the next reaction without further purification.

(E, Z, E) -2,4,7-tridecatrien-1-ol (15)
A 200 ml three-necked flask was charged with ethyl (E, Z, E) -2,4,7-tridecatrienoate (14) (1.0 g of crude product, 4.23 mmol) and diethyl ether (50 ml) at −78 ° C. The mixture was stirred under a nitrogen atmosphere while being cooled. Diisobutylaluminum hydride (DIBAL) (toluene solution) (0.99 M, 9.4 ml, 9.3 mmol) was dropped into the system, and the mixture was stirred for 1.0 hour while removing the dry ice bath and raising the temperature to room temperature. After confirming disappearance of the raw materials, 10% Rochelle salt aqueous solution (100 ml) was added to the system and stirred overnight. After the separation operation, the aqueous layer was extracted with diethyl ether, combined with the previous organic layer, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration under reduced pressure, the residue obtained by concentrating the filtrate under reduced pressure (0.95 g) was purified by silica gel chromatography (100 g, hexane: ethyl acetate = 10: 1), and (E, Z, E) -2, 4,7-tridecatrien-1-ol (15) (600 mg, yield 59% (2 steps)) was obtained.

(E, Z, E) -2,4,7-Tridecatrienal (3)
To a 50 ml eggplant flask was added (E, Z, E) -tridecatrien-1-ol (15) (300 mg, 1.54 mmol), manganese dioxide (4.03 g, 46.3 mmol) and methylene chloride (25 ml). Stir at room temperature overnight. After confirming the disappearance of the raw materials and filtration under reduced pressure, the residue obtained by concentrating the filtrate under reduced pressure (280 mg) was purified by silica gel chromatography (30 g, hexane: ethyl acetate = 100: 1), and (E, Z, E) -2,4,7-tridecatrienal (3) (248 mg, 85%) was obtained (purity 94.1%).

(Example 3) Preparation of (E, E, E) -2,4,7-tridecatrienal (E, E, E) -2,4,7- of formula (4) according to the following series of reaction formulas Tridecatrienal was synthesized. The percentage in parentheses below the process number indicates the yield of each process.

(E, E) -2,5-Undecadien-1-ol (16)
A 1 L eggplant flask was charged with lithium aluminum hydride (3.20 g, 84.2 mmol) and diethyl ether (300 ml), and stirred while cooling in an ice bath. Into the system, a solution of (E) -undec-5-en-2-yn-1-ol (12) (14 g, crude product) obtained in Example 2 in diethyl ether (60 ml) was carefully added dropwise. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at reflux for 6.5 hours. Since it was confirmed that the raw material remained, lithium aluminum hydride (1.0 g, 26.3 mmol) was further added, and the mixture was further stirred at reflux for 8.0 hours. After confirming disappearance of the raw material, water (22 g) was carefully added while cooling in an ice bath. After stirring at room temperature for 30 minutes, a 2N aqueous hydrochloric acid solution was added to the system until the suspension became a clear two-layer system. After the liquid separation operation, the aqueous layer was extracted with ethyl acetate, washed with water, a saturated aqueous sodium hydrogen carbonate solution and a saturated saline solution together with the previous organic layer, and dried over anhydrous magnesium sulfate. After filtration under reduced pressure, 6.0 g of the residue (12.5 g) obtained by concentrating the filtrate under reduced pressure was used for the one-pot oxidation Wittig reaction of the next reaction.

  The remaining 6.0 g was purified by silica gel chromatography (1200 g, hexane: ethyl acetate = 10: 1) to give (E, E) -2,5-undecadien-1-ol (16) (3.04 g, yield). 70%).

Ethyl (E, E, E) -2,4,7-tridecatrienoate (17)
(E, E) -2,5-Undecadien-1-ol (16) (6.0 g, crude product) and methylene chloride (300 ml) were added to a 500 ml eggplant flask and stirred. Ethyl (triphenylphosphoranylidene) acetate (62.2 g, 178.5 mmol) was added to the system, and after confirming dissolution, manganese dioxide (31 g, 357 mmol) was added. After stirring at room temperature for 95 hours, the disappearance of the raw materials was confirmed, and silica gel (300 g) was added to the filtrate obtained by filtration under reduced pressure, followed by concentration under reduced pressure. The crude purified product obtained as a residue was purified by silica gel chromatography (200 g, hexane: ethyl acetate = 20: 1) using a silica gel adsorbed to obtain a crude purified product (5.2 g). This crude product was used in the next reaction without further purification.

(E, E, E) -2,4,7-tridecatrien-1-ol (18)
A 200 ml three-necked flask was charged with ethyl (E, E, E) -2,4,7-tridecatrienoate (17) (2.0 g, crude product) and diethyl ether (100 ml), and cooled to -78 ° C. The mixture was stirred under a nitrogen atmosphere. Diisobutylaluminum hydride (DIBAL) (toluene solution) (0.99 M, 19 ml, 18.7 mmol) was dropped into the system, and the mixture was stirred for 1.0 hour while the dry ice bath was removed and the temperature was raised to room temperature. After confirming disappearance of the raw materials, 10% Rochelle salt aqueous solution (100 ml) was added to the system and stirred overnight. After the separation operation, the aqueous layer was extracted with diethyl ether, combined with the previous organic layer, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration under reduced pressure, the residue obtained by concentrating the filtrate under reduced pressure (2.3 g) was purified by silica gel chromatography (400 g, hexane: ethyl acetate = 10: 1), and (E, E, E) -2, 4,7-tridecatrien-1-ol (18) (1.34 g, yield 50%, 2 steps) was obtained.

(E, E, E) -2,4,7-Tridecatrienal (4)
In a 50 ml eggplant flask, (E, E, E) -2,4,7-tridecatrien-1-ol (18) (347 mg, 1.79 mmol), manganese dioxide (4.67 g, 53.7 mmol) and methylene chloride (25 ml) was added and stirred at room temperature overnight. After confirming the disappearance of the raw materials and filtering under reduced pressure, the residue (314 mg) obtained by concentrating the filtrate under reduced pressure was purified by silica gel chromatography (40 g, hexane: ethyl acetate = 100: 1), and (E, E, E) -2,4,7-tridecatrienal (4) (289 mg, 84%) was obtained (purity 96.3%).

(Example 4) Preparation of (E, Z) -4,7-tridecadienal (E, Z) -4,7-tridecadienal of formula (5) was synthesized according to the following series of reaction formulas. . The percentage in parentheses below the process number indicates the yield of each process.

2-Octin-1-ol (20)
2-Propin-1-ol (4.68 g, 83.5 mmol) and tetrahydrofuran (80 mL) were charged into a 500 mL four-necked flask, and the mixture was cooled and stirred at −40 ° C. in a nitrogen atmosphere. Next, a butyllithium / hexane solution (1.67 M, 100 mL, 167 mmol) was dropped into the system over 30 minutes, and the mixture was stirred for 1 hour while being heated to −20 ° C. After cooling again to −40 ° C., a 1,3-dimethyl-2-imidazolidinone (DMI) solution (80 mL) of 1-bromopentane (19) (11.98 g, 79.3 mmol) was added dropwise for 30 minutes. After completion of the dropwise addition, the mixture was stirred overnight. After completion of the stirring, a saturated aqueous ammonium chloride solution was added and stirred for further 15 minutes to complete the reaction. After the reaction solution was transferred to a separatory funnel and the organic layer was removed, the aqueous layer was extracted with ethyl acetate, combined with the previous organic layer, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration under reduced pressure, the filtrate was concentrated under reduced pressure using an evaporator, and the resulting residue was purified by silica gel chromatography (200 g, hexane: ethyl acetate = 10: 1 to 3: 1) to give 2-octyne-1- All (20) (7.1 g, 71% yield) was obtained.

1-Bromo-2-octyne (21)
2-Octin-1-ol (20) (7.1 g, 56.3 mmol), ether (70 mL) and pyridine (210 mg) were charged into a 200 mL eggplant flask and stirred at room temperature. Phosphorus tribromide (5.75 g, 21.3 mmol) was added dropwise to the system over 30 minutes, and the mixture was stirred at room temperature for 3 hours. After confirming disappearance of the raw material by gas chromatography by sampling the reaction solution, a saturated aqueous sodium hydrogen carbonate solution was added to the system and stirred for 30 minutes to complete the reaction. After the reaction solution was transferred to a separatory funnel and the organic layer was removed, the aqueous layer was extracted with diethyl ether, combined with the previous organic layer, washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and over anhydrous magnesium sulfate. Dried. After filtration under reduced pressure, the filtrate was concentrated under reduced pressure with an evaporator, and the resulting residue was purified by distillation under reduced pressure to give 1-bromo-2-octyne (21) (6.75 g, yield 63%, boiling point 66- 67 ° C./10 mmHg).

2,5-Undecadiin-1-ol (22)
An ethylmagnesium bromide / tetrahydrofuran solution (1.0 M, 106 mL, 106 mmol) was charged into a 500 mL four-necked flask and stirred while cooling in an ice bath under a nitrogen atmosphere. A tetrahydrofuran solution (20 mL) of 2-propyn-1-ol (2.96 g, 52.8 mmol) was added dropwise. After stirring at room temperature for 1.5 hours, the mixture was cooled again using an ice bath. Copper (I) cyanide (1.33 g) was added to the system, and after stirring for 15 minutes, a tetrahydrofuran solution (20 mL) of 1-bromo-2-octyne (21) (5.0 g, 26.4 mmol) was added dropwise. After removing the water bath and stirring at reflux for 2 hours, 2N aqueous hydrochloric acid was added to the system to terminate the reaction. The reaction solution was transferred to a separatory funnel, the organic layer was removed, and the aqueous layer was extracted with ether. The organic layer was washed with water, 2N hydrochloric acid aqueous solution, saturated aqueous sodium hydrogen carbonate solution and brine successively. And dried over anhydrous magnesium sulfate. After filtration under reduced pressure, the filtrate was concentrated under reduced pressure using an evaporator, and the resulting residue was purified by silica gel chromatography (250 g, hexane: ethyl acetate = 20: 1) to obtain 2,5-undecadiin-1-ol ( 22) (3.37 g, 76% yield).

(E) -Undec-2-en-5-in-1-ol (23)
A solution of 1.89 g (50 mmol) of lithium aluminum hydride in 200 mL of diethyl ether and a solution of 8.21 g (50 mmol) of 2,5-undecadin-1-ol (22) (GC purity 86.4%) in 20 mL of diethyl ether Was added. Hydrogen gas was generated and generated heat to 25-30 ° C. under air cooling. Next, the mixture was heated and stirred for 2 hours under reflux (around 35 ° C.). After cooling with ice water, 10 g of water was carefully added dropwise. After stirring for 1 hour, the precipitate was filtered under reduced pressure. The filtrate was concentrated and 7.4 g of the residue was purified by silica gel chromatography (silica gel 200 mL, hexane: ether = 3: 1 to 1: 1), and (E) -undec-2-en-5-in-1- All (23) was obtained (5.1 g, yield 61.4%, GC purity 94.2%). ^{By 1} H-NMR, the vicinal coupling constant between olefinic hydrogen was 15.2 Hz, and it was confirmed to be an E-olefin.

(E, Z) -2,5-Undecadien-1-ol (24)
(E) -Undec-2-en-5-in-1-ol (23) 100 mg of Lindlar catalyst (manufactured by NEM Chemcat) was added to a solution of 1.00 g of ethyl acetate, and the mixture was stirred under hydrogen for 5 hours. did. When the reaction solution was followed by gas chromatography over time, it was observed that the reaction gradually progressed and changed into the compound (24). After the reaction, the residue obtained by filtration through celite and concentration was purified by silica gel chromatography (silica gel 30 g, hexane: diethyl ether = 3: 1 to 1: 1), and (E, Z) -2,5- Undecadien-1-ol (24) was obtained (0.89 g, yield 87.9%). From TC-1 GC (FID), DB-1701 GC-MS (TCI), and NMR, no signal that appeared to be a superreduced product was observed.

Methyl 2-methoxycarbonyl- (E, Z) -4,7-tridecadienoate (25)
To a solution of (E, Z) -2,5-undecadien-1-ol (24) 90 mg (0.535 mmol), methylene chloride 5 mL, triethylamine 224 μL (1.607 mmol), methanesulfonic acid chloride 62 μL (with cooling with ice water) 0.801 mmol) was added. After 1.5 hours, the mixture was diluted with diethyl ether and washed twice with water, an aqueous ammonium chloride solution, and brine twice. After concentration, 200 mg of crude mesylate was obtained.

  Separately, 85 mg (0.757 mmol) of potassium t-butoxide was added to 5 mL of N, N-dimethylformamide in 100 mg (0.757 mmol) of dimethyl malonate. This solution was cooled with ice water, and 200 mg of the crude mesylate prepared above in 5 mL of N, N-dimethylformamide was added over 5 minutes. The mixture was stirred overnight while warming to room temperature. Water was added (pH = 8) and extracted twice with diethyl ether. After washing twice with brine and concentrating, 130 mg of crude product was obtained. This was purified by silica gel chromatography (silica gel 30 g, hexane: diethyl ether = 4: 1) to obtain methyl 2-methoxycarbonyl- (E, Z) -4,7-tridecadienoate (25) ( 82 mg, yield 54.4%).

Methyl (E, Z) -4,7-tridecadienoate (26)
In a 50 ml eggplant flask, methyl 2-methoxycarbonyl- (E, Z) -4,7-tridecadienoate (25) (1.53 g, 5.43 mmol), sodium chloride (0.63 g, 10.77 mmol), water (0.63 g) and dimethyl sulfoxide (DMSO) (10 ml) were charged and stirred for 2.5 hours while heating to 180 ° C. Water was added to the system and the organic layer obtained by diethyl ether extraction was washed with saturated brine. After drying over anhydrous magnesium sulfate, the residue obtained by filtration under reduced pressure and concentration under reduced pressure was purified by silica gel chromatography (50 g, hexane: ethyl acetate = 20: 1-10: 1), and methyl (E, Z) -4 , 7-tridecadienoate (26) (0.85 g, 70% yield) was obtained.

(E, Z) -4,7-Tridecadien-1-ol (27)
A 100 ml eggplant flask was charged with lithium aluminum hydride (135 mg, 3.57 mmol) and diethyl ether (15 ml) and stirred while cooling with ice. A solution of methyl (E, Z) -4,7-tridecadienoate (26) (800 mg, 3.57 mmol) in diethyl ether (15 ml) was carefully added dropwise to the system and stirred while gradually raising the temperature. After confirming the disappearance of the raw material by TLC, it was ice-cooled again, and water (0.71 g) was carefully added to the system and vigorously stirred. After stirring until the reaction mixture became a white slurry, the filtrate obtained by vacuum filtration was concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography (50 g, hexane: ethyl acetate = 2: 1 to 1: 1) (E, Z) -4,7-tridecadien-1-ol (27) (620 mg, yield). 89%).

(E, Z) -4,7-tridecadienal (5)
A 100 ml eggplant flask was charged with (E, Z) -4,7-tridecadien-1-ol (27) (590 mg, 3.01 mmol) and methylene chloride (30 ml), and dimethyl phosphate (1.53 g, 3.61 mmol) was added. After stirring for 2.0 hours, the remaining of the raw material was confirmed by thin layer chromatography, and dimethyl phosphate (500 mg) was further added. After confirming the disappearance of the raw material by thin layer chromatography again, a 10% aqueous sodium sulfate solution was added to the system and stirred for 30 minutes. After the liquid separation operation, the aqueous layer was extracted with diethyl ether. The obtained organic layer and the previous organic layer were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtration under reduced pressure, the residue obtained by concentrating the filtrate under reduced pressure was purified by silica gel chromatography (50 g, hexane: ethyl acetate = 9: 1), and (E, Z) -4,7-tridecadienal (5 ) (475 mg, 81% yield).

Example 5 Preparation of (Z, E) -4,7-tridecadienal (Z, E) -4,7-tridecadienal of formula (6) was synthesized according to the following series of reaction formulas. . The percentage in parentheses below the process number indicates the yield of each process.

(E) -Trideca-7-en-4-yn-1-ol (28)
A 300 mL flask was charged with ethylmagnesium bromide / tetrahydrofuran (0.9M, 100 ml, 90 mmol) and stirred at room temperature under a nitrogen atmosphere. A solution of 4-pentyn-1-ol (3.8 g, 45 mmol) in tetrahydrofuran (10 ml) was added dropwise thereto, and the mixture was stirred at 60 ° C. for 0.5 hour, and then returned to room temperature. Copper cyanide (1.0 g) was added to the system, and after stirring for 15 minutes at 5 to 10 ° C., (E) -1-bromooct-2-ene (11) (9.2 g, 45 mmol, prepared in Example 2) was prepared. Crude product) Tetrahydrofuran (10 ml) solution was added dropwise. After dropping, the mixture was stirred overnight at room temperature. The reaction solution is poured into a saturated aqueous solution of sodium hydrogen carbonate, and after separation, the aqueous layer is extracted with diethyl ether, and combined with the previous organic layer, washed successively with a dilute hydrochloric acid solution, a saturated aqueous solution of sodium bicarbonate, and saturated brine, Dried with magnesium sulfate. After filtration under reduced pressure, the residue obtained by concentrating the filtrate under reduced pressure (10 g) was purified by distillation under reduced pressure and silica gel chromatography (300 g, hexane: ethyl acetate = 4: 1 to 3: 2), and (E) -Trideca -7-en-4-yn-1-ol (28) (1.0 g, 11%) was obtained.

(Z, E) -4,7-Tridecadien-1-ol (29)
In a 50 ml flask was added (E) -tridec-7-en-4-yn-1-ol (28) (1.0 g, 5.1 mmol), quinoline (1 drop), 1-hexene (30 mL) and Lindlar catalyst (N (E-Chemcat) (20 mg) was charged, and the mixture was stirred for 3.0 hours under ice-cooling and hydrogen atmosphere. After confirming the disappearance of the raw materials by gas chromatography, the reaction solution was diluted with hexane and then filtered to obtain 1.0 g of a crude product. The obtained crude product was purified by silica gel chromatography (200 g, hexane: ethyl acetate = 30: 1), and (Z, E) -4,7-tridecadien-1-ol (29) (604 mg, 60%). )

(Z, E) -4,7-Tridecadienal (6)
2-Iodoxybenzoic acid (IBX) (1.3 g, 5.4 mmol) and dimethyl sulfoxide (DMSO) (15 mL) were charged into a 30 mL flask, and the mixture was stirred at room temperature for 40 minutes. After confirming the dissolution of IBX, (Z, E) -4,7-tridecadien-1-ol (29) (600 mg, 3.1 mmol) was added, and the mixture was stirred at room temperature for 4 hours. Water was added to the reaction solution, and the mixture was stirred for 30 minutes, filtered and washed with hexane. The filtrate was extracted with ether, combined with the previous organic layer, washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and anhydrous magnesium sulfate. Dried. After filtration under reduced pressure, the residue obtained by concentrating the filtrate under reduced pressure (600 mg) was purified by silica gel column chromatography (200 g, hexane: ethyl acetate = 30: 1) to give (Z, E) -4,7-trideca. Dienal (6) (10 mg, 17% yield) was obtained.

(Example 6) Preparation of (E, E) -4,7-tridecadienal (E, E) -4,7-tridecadienal of formula (7) was synthesized according to the following series of reaction formulas. . The percentage in parentheses below the process number indicates the yield of each process.

(E, E) -4,7-Tridecadien-1-ol (30)
Liquid ammonia (60 ml) was stored in a 200-ml three-neck flask with a cold finger cooled in a dry ice-acetone bath, and lithium metal (458 mg, 66 mmol) was added and stirred for 1.0 hour to confirm dissolution of lithium. Into the system, (E) -tridec-7-en-4-yn-1-ol (28) (850 mg, 4.4 mmol) obtained in Example 5 in diethyl ether (8 ml) and t-butyl alcohol (8 ml) ) And the mixture was stirred overnight while gradually raising the temperature. The next morning, a 10% aqueous sodium thiosulfate solution was added and stirred for 30 minutes, followed by concentration under reduced pressure to remove residual ammonia. The organic layer obtained by extracting the aqueous layer of the residue with diethyl ether was washed successively with water and a saturated saline solution, and dried over anhydrous magnesium sulfate. After filtration under reduced pressure, the residue obtained by concentrating the filtrate under reduced pressure was purified by silica gel chromatography (85 g, hexane: ethyl acetate = 10: 1), and (E, E) -4,7-tridecadien-1-ol. (30) (630 mg, 73% yield) was obtained.

(E, E) -4,7-Tridecadienal (7 )
A 100 ml eggplant flask was charged with (E, E) -4,7-tridecadien-1-ol (30) (300 mg, 1.53 mmol), sodium bicarbonate (1.3 g) and methylene chloride (30 ml) and stirred with ice cooling. did. Dess-Martin periodinane (DMP) (1.3 g, 3.06 mmol) was added to the system and stirred for 2.0 hours. After confirming disappearance of the raw materials, a 10% aqueous sodium thiosulfate solution was added to the system and stirred for 1.0 hour. After separation operation, the aqueous layer was extracted with diethyl ether, combined with the previous organic layer, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration under reduced pressure, the residue obtained by concentrating the filtrate under reduced pressure was purified by silica gel chromatography (30 g, hexane: ethyl acetate = 100: 1), and (E, E) -4,7-tridecadienal ( 7) (256 mg, 86%) was obtained.

(Reference Example 1) Preparation of Ramen Soup Ramen soup was prepared according to the formulation shown in Table 1 as an evaluation system for the taste enhancing effect of the unsaturated aldehyde of the present invention.

(Example 7) Addition of (E, E, Z) -2,4,7-tridecatrienal to ramen soup (E, E, Z) -2,4,7-tridecatrienal in ramen soup Sensory evaluation was performed by 10 trained panelists, with the contents added as shown in Table 2 and the taste-added agent-free product as a control. The evaluation results are shown in Table 2.

As shown in Table 2, the addition of 10 ⁻³ ppb to 10 ⁴ ppb (10 ppm) of (E, E, Z) -2,4,7 ^- tridecatrienal increases the taste of ramen soup. Was shown to do. As the addition amount of (E, E, Z) -2,4,7 ^- tridecatrienal, about 10 ⁻² ppb to 10 ³ ppb was particularly good. In addition, although umami | taste increased by 100 ppm addition, the aldehyde-like fragrance peculiar to (E, E, Z) -2,4,7-tridecatrienal was also felt somewhat. Some panelists felt that the taste was slightly increased even at a low concentration of 10 ⁻³ ppb, and it was found that the effect of enhancing the taste was enhanced even at a low concentration.

(Example 8) Addition of (E, Z, E) -2,4,7-tridecatrienal to ramen soup (E, Z, E) -2,4,7-tridecatrienal in ramen soup Sensory evaluation was performed by 10 trained panelists, with the contents added as shown in Table 3 and the taste enhancer-free product as a control. The evaluation results are shown in Table 3.

As shown in Table 3, by adding ^10-3 ppb to 10 ⁴ ppb (10 ppm) of (E, Z, E) -2,4,7-tridecatrienal to ramen soup, the taste is increased. Was shown to do. As the amount of (E, Z, E) -2,4,7-tridecatrienal added, about 10 ⁻² ppb to 10 ³ ppb was particularly good. In addition, although umami | taste increased by 100 ppm addition, the aldehyde-like fragrance peculiar to (E, Z, E) -2,4,7-tridecatrienal was also felt somewhat. Some panelists felt that the taste was slightly increased even at a low concentration of 10 ⁻³ ppb, and it was found that the effect of enhancing the taste was enhanced even at a low concentration.

(Example 9) Addition of (E, E, E) -2,4,7-tridecatrienal to ramen soup (E, E, E) -2,4,7-tridecatrienal in ramen soup Sensory evaluation was performed by 10 trained panelists, with the contents added as shown in Table 4 and the taste enhancer-free product as a control. The evaluation results are shown in Table 4.

As shown in Table 4, by adding ^10-3 ppb to 10 ⁴ ppb (10 ppm) of (E, E, E) -2,4,7-tridecatrienal to ramen soup, the umami taste increases. Was shown to do. As the addition amount of (E, E, E) -2,4,7 ^- tridecatrienal, about 10 ⁻² ppb to 10 ³ ppb was particularly good. In addition, although umami | taste increased by 100 ppm addition, the aldehyde-like fragrance peculiar to (E, E, E) -2,4,7-tridecatrienal was also felt somewhat. Some panelists felt that the taste was slightly increased even at a low concentration of 10 ⁻³ ppb, and it was found that the effect of enhancing the taste was enhanced even at a low concentration.

(Example 10) Addition of (E, Z) -4,7-tridecadienal to ramen soup The content of (E, Z) -4,7-tridecadienal in ramen soup is shown in Table 5, respectively. Sensory evaluation was performed by 10 trained panelists, with the addition of the indicated values and the taste additive-free product as a control. The evaluation results are shown in Table 5.

As shown in Table 5, the addition of 10 ⁻³ ppb to 10 ⁴ ppb (10 ppm) of (E, Z) -4,7-tridecadienal to ramen soup may increase the taste. Indicated. As the addition amount of (E, Z) -4,7 ^- tridecadienal, about 10 ⁻² ppb to 10 ³ ppb was particularly good. In addition, although umami | taste increased by 100 ppm addition, the aldehyde-like fragrance peculiar to (E, Z) -4,7-tridecadienal was also felt somewhat. Some panelists felt that the taste was slightly increased even at a low concentration of 10 ⁻³ ppb, and it was found that the effect of enhancing the taste was enhanced even at a low concentration.

(Example 11) Addition of (Z, E) -4,7-tridecadienal to ramen soup The contents of (Z, E) -4,7-tridecadienal in ramen soup are shown in Table 6 respectively. Sensory evaluation was performed by 10 trained panelists, with the addition of the indicated values and the taste additive-free product as a control. The evaluation results are shown in Table 6.

As shown in Table 6, the taste of umami may be increased by adding 10 ⁻³ ppb to 10 ⁴ ppb (10 ppm) of (Z, E) -4,7-tridecadienal to ramen soup. Indicated. The amount of (Z, E) -4,7 ^- tridecadienal added was particularly good at about 10 ⁻² ppb to 10 ³ ppb. In addition, although umami | taste increased by 100 ppm addition, the aldehyde-like fragrance peculiar to (Z, E) -4,7-tridecadienal was also felt somewhat. Some panelists felt that the taste was slightly increased even at a low concentration of 10 ⁻³ ppb, and it was found that the effect of enhancing the taste was enhanced even at a low concentration.

(Example 12) Addition of (E, E) -4,7-tridecadienal to ramen soup The contents of (E, E) -4,7-tridecadienal in ramen soup are shown in Table 7 respectively. Sensory evaluation was performed by 10 trained panelists, with the addition of the indicated values and the taste additive-free product as a control. The evaluation results are shown in Table 7.

As shown in Table 7, the addition of 10 ⁻³ ppb to 10 ⁴ ppb (10 ppm) of (E, E) -4,7-tridecadienal to ramen soup may increase the taste. Indicated. The amount of (E, E) -4,7 ^- tridecadienal added was particularly good at about 10 ⁻² ppb to 10 ³ ppb. In addition, although umami | taste increased by 100 ppm addition, the aldehyde-like fragrance peculiar to (E, E) -4,7-tridecadienal was also felt somewhat. Some panelists felt that the taste was slightly increased even at a low concentration of 10 ⁻³ ppb, and it was found that the effect of enhancing the taste was enhanced even at a low concentration.

(Example 13) Addition of unsaturated aldehyde to sodium glutamate-reduced ramen soup According to the formulation in Table 8, a normal ramen soup and a ramen soup in which the amount of sodium L-glutamate (MSG) used was reduced to 2/3 of the usual amount did. The MSG-reduced ramen soup was prepared by adding 10 ppb each of the unsaturated aldehydes of the present invention, and these were subjected to sensory evaluation by 10 trained panelists. As the evaluation criteria for sensory evaluation, the following criteria were used, with 10 points being the perfect score for each of richness, richness, saltiness, complexity, naturalness, and fragrance. The sensory evaluation was performed as very good: 10 points, good: 8 points, slightly good: 6 points, slightly bad: 4 points, bad: 2 points, very bad: 0 points. The average score of the evaluation is shown in Table 9.

  As shown in Table 9, the ramen soup with reduced MSG has a sensory evaluation deeply related to taste such as richness, richness, saltiness, and complexity, compared to normal ramen soup. Evaluation was bad compared with. Moreover, it was evaluation that it was inferior also about a natural feeling. On the other hand, there was almost no difference in fragrance. On the other hand, the ramen soup with reduced MSG to which the unsaturated aldehyde of the present invention is added has a sensory evaluation deeply related to taste such as richness, richness, salty taste, complexity, etc. Each of the feelings was evaluated to be almost the same as that of ordinary ramen soup. In addition, the fragrance was better than that of ordinary ramen soup. Therefore, it was shown that the addition of the unsaturated aldehyde of the present invention enhances the taste of food and drink such as richness, richness, saltiness and complexity.

(Example 14) Preparation of taste enhancer powder In each unsaturated aldehyde of the present invention, 0.1 g of medium chain fatty acid triglyceride and 30 g of SAIB were mixed and dissolved to obtain an oil phase part. On the other hand, 680 g of soft water has a Paindex No. 2 was dissolved by adding 900 g of HLB15 and 50 g of sucrose fatty acid ester of HLB15, and sterilized by heating at 85 ° C. for 15 minutes. After cooling this solution to about 40 ° C., 50 g of the oil phase part prepared above is added while stirring and mixing with a TK-homomixer (made by Tokushu Kika Kogyo Co., Ltd.), and further stirred and mixed at 5000 rpm for 5 minutes. And 1690 g of an emulsified liquid was obtained. This emulsion was dried using a spray dryer (manufactured by NIRO: Mobile Miner) at an air blowing temperature of 150 ° C. and an exhaust air temperature of 80 ° C. to obtain 950 g of a taste enhancer powder.
Invention product 1: (E, E, Z) -2,4,7-tridecatrienal 0.01% by mass Invention product 2: (E, Z, E) -2,4,7-tridecatrienal Invention product 3 containing 0.01% by mass: (E, E, E) -2,4,7-tridecatrienal invention product containing 0.01% by mass: (E, Z) -4,7-tri The present invention product 5 containing 0.01% by mass of decadienal: The present product 6 containing 0.01% by mass of (Z, E) -4,7-tridecal 6: (E, E) -4,7-tri Decadienal 0.01% by mass (Example 15) Addition of unsaturated aldehyde of the present invention to noodle soup (powder type) Unsaturated taste enhancer of products 1 to 6 of commercial noodle soup (powder type) Add 0.02% by mass so that the aldehyde content is 20 ppb and mix with powder. It was prepared end type). Ten grams of unsaturated aldehyde-added and non-added noodle soup was diluted to 200 ml with hot water (1 ppb in drinking noodle soup), and sensory evaluation was performed by 10 trained panelists, with no taste enhancer added as a control. . The evaluation results are shown in Table 10.

  As shown in Table 10, the majority of the 10 panelists evaluated the addition of the product of the present invention that the soy sauce soup had a slightly or significantly increased umami taste such as richness, richness and complexity.

(Example 16) Addition of unsaturated aldehyde of the present invention to mayonnaise 60 g of water, 60 g of high acidity vinegar (acidity 10%), 60 g of fructose glucose mixed liquid sugar (Bx75 °), 80 g of frozen egg yolk, salt Add 0g, 1.0g of chemical seasoning and 10g of powdered spice, and uniformly stir and mix, then gradually add 723g of soybean oil, stir and mix uniformly, heat to 90 ° C, cool, and stir and deaerate and mix Got regular mayonnaise.

  On the other hand, in a cooking mixer 60 g of water, 60 g of high acidity vinegar (acidity 10%), 60 g of fructose glucose mixed liquid sugar (Bx75 °), 80 g of frozen egg yolk, 6.0 g of salt, 1.0 g of chemical seasoning, 10 g of powdered spice, and After adding 223 g of a thickener aqueous solution (containing kappa carrageenan 0.3%, xanthan gum 1.5% and maltodextrin 3%) and uniformly stirring and mixing, 500 g of soybean oil was gradually added and uniformly stirring and mixing, followed by 90 ° C. The mixture was stirred and degassed and mixed to obtain a low-fat mayonnaise (a reduction in fat content of about 30%).

  Furthermore, low fat mayonnaise was prepared by adding 1 ppb of the unsaturated aldehyde of the present invention, and these were subjected to sensory evaluation by 10 trained panelists. As evaluation criteria for sensory evaluation, each of the richness, kokumi, saltiness, complexity, naturalness, and fragrance was evaluated according to the following criteria, with 10 points each being a perfect score. The sensory evaluation was performed as very good: 10 points, good: 8 points, slightly good: 6 points, slightly bad: 4 points, bad: 2 points, very bad: 0 points. The average score of the evaluation is shown in Table 11.

  As shown in Table 11, mayonnaise with reduced fat compared to normal mayonnaise, all sensory evaluations deeply related to taste, such as richness, richness, salty taste, and complexity, compared to normal mayonnaise. Evaluation was bad and it was evaluation that natural feeling was also inferior. Also, the scent was slightly inferior. On the other hand, the low-fat mayonnaise to which the unsaturated aldehyde of the present invention is added has a sensory evaluation deeply related to taste such as richness, kokumi, salty taste, and complexity, as well as natural sense and fragrance, compared to normal mayonnaise. In all cases, the score was greatly improved compared to the low-fat mayonnaise with no additive, and it approached normal mayonnaise. Therefore, it was shown that the addition of the unsaturated aldehyde of the present invention enhances the taste of food and drink such as richness, richness and complexity.

Reference Example 1 Preparation of Bonito Flavor by Steam Distillation Into a 5 liter steam distillation kettle was charged 200 g of dried bonito and 1800 g of water, steam was blown from the bottom of the kettle, and steam distilled at about 100 ° C. for about 3 hours. went. The steam containing the volatile fragrance component distilled out was introduced into a water-cooled glass condenser, cooled to about 20 ° C., and condensed to obtain 400 g of recovered scent. 40 g of ODO (registered trademark: trade name of medium chain fatty acid triglyceride manufactured by Nisshin Oillio Co., Ltd.) 40 g was added to 400 g of the obtained recovered fragrance, followed by stirring and extraction at room temperature for 30 minutes. After extraction, the mixture was allowed to stand for 60 minutes, and the oil layer was decanted, dehydrated with anhydrous sodium sulfate, and filtered through filter paper to obtain 38 g of bonito flavor (reference product 1).

Reference Example 2 Preparation of Skipjack Bun Flavor by Extraction with Hydrous Alcohol 200 g of bonito bonito pulverized product and 100 g of 80% hydrous alcohol were added to a 3 liter flask, and the mixture was extracted by stirring at 80 to 85 ° C. for 3 hours. After extraction, the mixture was centrifuged and filtered to obtain 800 g of an extract, and alcohol was recovered under reduced pressure to obtain 15 g of bonito flavor (reference product 2).

(Reference Example 3) Preparation of Skipjack Bun Flavor by Preparation of Perfume Compound The following components were prepared (Reference 3)
4-Ethylguaiacol 1 part by mass 2,6-dimethoxyphenol 0.5
1,2-dimethoxy-4-propylbenzene 2
4-ethyl-2,6-dimethoxyphenol 1
Eugenol 0.5
Cis-3-hexenal 0.9
Cycloten 1
3-hexanone 1
6-Methyl-5-hepten-2-one 2
2-Methylindole 0.5
2-Ethyl-3,5-dimethylpyrazine 3
2-Ethyl-3,5-dimethoxypyrazine 2.4
2,4-dimethylthiazole 1
2,3-Dimethylbenzopyran 1
Furfuryl alcohol 0.1
Maltol 1
3,4,5-trimethyl-2- (3H) -furanone 1
Methanethiol 0.1
Total 20.0

(Reference example 4) Preparation of bonito-like blended fragrance composition As the bonito-like blended fragrance composition, the following components (parts by mass) were prepared (Comparative product 1).

Reference product 1 10 parts by mass Reference product 2 25
Reference product 3 0.5
Alcohol 35
Water 29.5
Total 100

(Example 17) Addition of (E, E, Z) -2,4,7-tridecatrienal to bonito-like blended fragrance (E, E, Z) -2,4,7-tridecatrienal was added in the proportions listed in Table 12. Each blended fragrance was subjected to sensory evaluation by 10 trained panelists. As evaluation criteria for sensory evaluation, each of woody feeling, knot feeling, and strength was evaluated according to the following criteria, with 10 points each being a perfect score and 5 controls (comparative product 1). The sensory evaluation was performed as very good: 10 points, good: 8 points, slightly good: 6 points, slightly bad: 4 points, bad: 2 points, very bad: 0 points. In addition, regarding the off-flavor (soap feeling, citrus feeling), the control (comparative product 1) is 0 points, the same degree of control: 0 points, slightly felt: 2 points, slightly felt: 4 points, clearly felt: 6 points The sensory evaluation was carried out with an unpleasant odor of 8 points and an unpleasant odor of 10 points. The average score of the evaluation is shown in Table 12.

As shown in Table 12, with respect to dried bonito-like blended fragrance composition, (E, E, Z) -2,4,7- tridecanol Triester knurl the ^{10 -2 ppm, 0.1ppm, 10ppm,} 100ppm, and 1000ppm added The bonito-like fragrance composition is evaluated as having a bonito-like woody feeling and knotty feeling, and a good bonito-like odor is emphasized. Even if 10 ⁻² ppm is present in the fragrance composition, the bonito has a bonito taste It was a result that a sense of woody was given. On the other hand, the addition of 10 ⁻³ ppm was not much different from the addition, and the addition of 1% produced a citrus-like, soap-like, and deteriorated fat-like odor.

(Example 18) Addition of (E, Z, E) -2,4,7-tridecatrienal to a skipjack-like compounded fragrance (E, Z, E) ) -2,4,7-tridecatrienal was added in the proportions listed in Table 13. Each blended flavor was subjected to sensory evaluation in the same manner as in Example 17. The average score of the evaluation is shown in Table 13.

As shown in Table 13, with respect to dried bonito-like blended fragrance composition, (E, Z, E) -2,4,7- tridecanol Triester knurl the ^{10 -2 ppm, 0.1ppm, 10ppm,} 100ppm, and 1000ppm added The bonito-like fragrance composition is evaluated as having a bonito-like woody feeling and a feeling of bonito, and a good bonito-like fragrance is emphasized. Even when 10 ⁻² ppm is present in the fragrance composition, it is fragrant. The result was that a bonito-like woody feeling was added. On the other hand, the addition of 10 ⁻³ ppm was not much different from the addition, and the addition of 1% produced a citrus-like, soap-like, and deteriorated fat-like odor.

(Example 19) Addition of (E, E, E) -2,4,7-tridecatrienal to bonito-like blended fragrance (E, E, E) ) -2,4,7-tridecatrienal was added in the proportions listed in Table 14. Each blended flavor was subjected to sensory evaluation in the same manner as in Example 17. The average score of the evaluation is shown in Table 14.

As shown in Table 14, with respect to dried bonito-like blended fragrance composition, (E, E, E) -2,4,7- tridecanol Triester knurl the ^{10 -2 ppm, 0.1ppm, 10ppm,} 100ppm, and 1000ppm added The bonito-like fragrance composition is evaluated as having a bonito-like woody feeling and a feeling of bonito, and a good bonito-like fragrance is emphasized. Even when 10 ⁻² ppm is present in the fragrance composition, it is fragrant. The result was that a bonito-like woody feeling was added. On the other hand, the addition of 10 ⁻³ ppm was not much different from the addition, and the addition of 1% produced a citrus-like, soap-like, and deteriorated fat-like odor.

(Example 20) Addition of (E, Z) -4,7-tridecadienal to bonito-like blended fragrance (E, Z) -4,7 to bonito-like blended fragrance composition (Comparative product 1) -Tridecadienal was added in the proportions listed in Table 15. Each blended flavor was subjected to sensory evaluation in the same manner as in Example 17. The average score of the evaluation is shown in Table 15.

As shown in Table 15, bonito-like fragrance in which (E, Z) -4,7-tridecadienal was added to 10 ⁻² ppm, 0.1 ppm, 10 ppm, 100 ppm, and 1000 ppm to the bonito-like blended fragrance composition. The composition is evaluated as having a bonito-like woody feeling and a feeling of bonito, and a good bonito-like aroma is emphasized, and even when 10 ⁻² ppm is present in the fragrance composition, it is bonito-like The result was a feeling of woody. On the other hand, the addition of 10 ⁻³ ppm was not much different from the addition, and the addition of 1% produced a citrus-like, soap-like, and deteriorated fat-like odor.

(Example 21) Addition of (Z, E) -4,7-tridecadienal to bonito-like blended fragrance (Z, E) -4,7 to bonito-like blended fragrance composition (Comparative product 1) -Tridecadienal was added in the proportions listed in Table 16. Each blended flavor was subjected to sensory evaluation in the same manner as in Example 17. The average score of the evaluation is shown in Table 16.

As shown in Table 16, bonito-like fragrance in which (Z, E) -4,7-tridecadienal was added to 10 ⁻² ppm, 0.1 ppm, 10 ppm, 100 ppm, and 1000 ppm to the bonito-like blended fragrance composition The composition is evaluated as having a bonito-like woody feeling and a feeling of bonito, and a good bonito-like aroma is emphasized, and even when 10 ⁻² ppm is present in the fragrance composition, it is bonito-like The result was a feeling of woody. On the other hand, the addition of 10 ⁻³ ppm was not much different from the addition, and the addition of 1% produced a citrus-like, soap-like, and deteriorated fat-like odor.

(Example 22) Addition of (E, E) -4,7-tridecadienal to bonito-like compounded fragrance (E, E) -4,7 to bonito-like compounded fragrance composition (Comparative product 1) -Tridecadienal was added in the proportions listed in Table 17. Each blended flavor was subjected to sensory evaluation in the same manner as in Example 17. The average score of the evaluation is shown in Table 17.

As shown in Table 17, bonito-like fragrance in which (E, E) -4,7-tridecadienal was added to 10 ⁻² ppm, 0.1 ppm, 10 ppm, 100 ppm, and 1000 ppm to the bonito-like blended fragrance composition The composition is evaluated as having a bonito-like woody feeling and a feeling of bonito, and a good bonito-like aroma is emphasized, and even when 10 ⁻² ppm is present in the fragrance composition, it is bonito-like The result was a feeling of woody. On the other hand, the addition of 10 ⁻³ ppm was not much different from the addition, and the addition of 1% produced a citrus-like, soap-like, and deteriorated fat-like odor.

(Reference Example 5) Preparation of Skipjack Bun Extract 10 kg of skipjack knot was pulverized with a hammer mill (screen 3 mm), charged into a 50 L column extractor, and 50 kg of 10% ethanol aqueous solution heated to 60 ° C. from the top of the column was 50 kg / hour. The liquid was passed at a flow rate to obtain 35 kg of an extract, and after filtration, the filtrate was concentrated under reduced pressure to obtain 7 kg of a concentrated liquid (bonito extract) (reference product 4).

(Example 23) Preparation of bonito-flavored flavor seasoning Using reference product 4 (600 g), the seasoning material shown below and the diluted solution of the unsaturated aldehyde of the present invention were each added to 10 ppb and dissolved at 90 ° C. by heating. After cooling, the bonito seasoning seasoning was obtained.

Reference product 4 600 parts by mass Salt 40
Sodium glutamate 70
Sodium succinate 5
Granulated sugar 40
Nucleic acid seasoning 5
Plant protein hydrolyzate (HVP) 20
Yeast extract 10
Water 210
Total 1000
Each bonito-flavored seasoning was subjected to sensory evaluation by 10 trained panelists, using an unsaturated aldehyde-free product as a control. The average sensory evaluation results are shown in Table 18.

  As shown in Table 18, the addition of the unsaturated aldehyde of the present invention to the skipjack seasoned seasoning seasoned with the bonito seasoning without any unsaturated aldehyde added, It was evaluated that it had been given a good bonito-like flavor.

(Example 24) Preparation of bonito-like blended fragrance to which the unsaturated aldehyde of the present invention was added To the comparative product 1, 10 ppm each of the unsaturated aldehyde of the present invention was added to give a bonito-like blended fragrance of the present invention.

Invention product 7: 10 ppm of (E, E, Z) -2,4,7-tridecatrienal added to comparison product Invention product 8: (E, Z, E) -2,4, to comparison product 1 Addition of 10 ppm of 7-tridecatrienal Invention product 9: Addition of 10 ppm of (E, E, E) -2,4,7-tridecatrienal to comparison product 1 Invention product 10: Addition of (E, Z to comparison product 1) ) -4,7-tridecadienal added 10 ppm Invention product 11: Comparative product 1 added (Z, E) -4,7-tridecadienal 10 ppm added Product 12: comparative product 1 added (E , E) -4,7-tridecadienal 10 ppm added (Example 25) Mixing of bonito-like blended fragrance to bonito-flavored miso 100 parts by weight of frozen groundnut surimi, 2.5 parts by weight of sodium chloride, sodium L-glutamate 1.5 parts by mass, 1 part by mass of glycine, 0.1 parts by weight of Nantham, bonito-like blended fragrance composition obtained in Reference Example 4 and Example 24 (each one of Comparative Product 1 or Products 7 to 12 of the present invention) 0.2 parts by weight, potato starch 8 parts by weight, 11 parts by weight of egg white and 50 parts by weight of ice water (total 174.3.6 parts by weight) were kneaded and steamed at 95 ° C. for 40 minutes to prepare bonito-flavored miso.

  These bonito-flavored kamaboko were subjected to sensory evaluation by 10 trained panelists. As a result, all 10 trained panelists showed that the bonito-flavored kamaboko added with the bonito-like blended fragrance composition of the present invention was more bonito-like kamaboko than the bonito-flavored kamaboko added with the comparative product 1. The feeling was emphasized.

(Example 26) Preparation of powdered fragrance 70 g of gum arabic and 20 g of trehalose were added to 150 g of water and dissolved, and then heat sterilized at 85 to 90 ° C. for 15 minutes. After cooling this to 40 ° C., 10 g of the bonito-like blended fragrance composition obtained in Reference Example 4 and Example 24 (comparative product 1 or any one of the present invention products 7 to 12) was added and mixed. And emulsified with a TK-homomixer. This emulsified liquid was spray-dried at an inlet temperature of 140 ° C. and an outlet temperature of 75 ° C. using a mobile minor spray dryer manufactured by Niro Co., Ltd., and 95 g of bonito powder fragrance (comparative product 2 and inventive products 13 to 18 respectively) )

(Example 27) Mixing into bonito sprinkle sprinkle Commercial bonito sprinkle sprinkle (Oka) 0.1 g of bonito powder fragrance obtained in Example 26 (comparative product 2 or any one of invention products 13 to 18) And mixed well. These bonito sprinkles were subjected to sensory evaluation by 10 trained panelists. As a result, all 10 trained panelists emphasized the bonito-like woody and knot feelings of the bonito sprinkle with the invention products 13 to 18 compared to the bonito sprinkle with the comparison product 2 added. It was evaluated.

(Example 28) Blending into bonito seasoning dressing 46.6 parts by mass of water and 3 parts by mass of fructose-glucose liquid sugar were mixed, and here a powder mixture of 0.1 part by mass of gellan gum-containing preparation and 3 parts by mass of konjac processed product. Was added and dissolved by stirring at 80 ° C. for 10 minutes. Furthermore, 3 parts by weight of light soy sauce, 12 parts by weight of white soy sauce, 4 parts by weight of lemon juice transparent concentrated and reduced, 1 part by weight of sodium chloride, 0.3 parts by weight of sodium L-glutamate, bonito extract obtained in Reference Example 5 (reference product) 4) After adding 1 mass part and making it melt | dissolve, 6 mass parts of brewing vinegars (acidity 4.2%) and 5 mass parts of apple vinegar were added and stirred, and the water layer part was prepared. On the other hand, 14.9 parts by mass of corn salad oil as the oil layer part, and the bonito-like blended fragrance composition obtained in Reference Example 4 and Example 24 (comparative product 1 or any one of the present invention products 7-12) 0 .1 part by mass was stirred and mixed to prepare a total of 15 parts by mass of an oil layer part. Then, the container was filled and sterilized so that the water layer portion and the oil layer portion were in a ratio of 85:15 to prepare a bonito-flavored separate dressing (pH 3.8).

  These bonito-flavored dressings were subjected to sensory evaluation by 10 trained panelists. As a result, all 10 trained panelists emphasized the skipjack-like woody feeling and knot feeling of the bonito-flavored dressing with the addition of the inventive products 7-12 compared to the bonito-flavored dressing with the comparison product 1. Evaluated as being.

Claims (11)

Following formula ( 2 )

[In the formula, ... Represents a single bond or a double bond, and a wavy line represents a cis or trans configuration.] (However, (E, Z, Z) -2,4,7-tridecatrie Nar , (E, E, Z) -2,4,7-tridecatrienal, (E, E, E) -2,4,7-tridecatrienal and (Z, Z) -4,7-trideca The flavor improving agent which consists of unsaturated aldehyde represented by (except dienal). Following formula ( 2 )

[In the formula, ... Represents a single bond or a double bond, and a wavy line represents a cis or trans configuration.] (However, (E, Z, Z) -2,4,7-tridecatrie Nar , (E, E, Z) -2,4,7-tridecatrienal, (E, E, E) -2,4,7-tridecatrienal and (Z, Z) -4,7-trideca A taste enhancer for foods and drinks comprising an unsaturated aldehyde represented by the following formula (excluding dienal): The food / beverage taste enhancer according to claim 2, wherein the food / beverage product is a food / beverage product having a delicious taste. The taste enhancer for foods and beverages according to claim 2 or 3, wherein the taste enhancement is enhancement of taste. The food / beverage product having a delicious taste is a food / beverage product containing one or more selected from amino acids, nucleic acids, organic acids, oils and fats, and sodium chloride. The taste enhancer for foods and beverages according to item 1. Following formula (1)

[In the formula,... Represents a single bond or a double bond, and a wavy line represents a cis or trans configuration.] (However, (E, Z, Z) -2,4,7-tridecatrienal, (E, E, Z) -2,4,7-tridecatrienal, (E, E, E) -2,4,7-tridecatrienal, and (Z, Z) -4,7-tridecadiere A food / beverage product comprising 10 ⁻² ppm to 10 ⁴ ppm of an unsaturated aldehyde represented by the formula (1) as an unsaturated aldehyde represented by formula (1). Taste enhancer composition.
Following formula (1)

[In the formula,... Represents a single bond or a double bond, and a wavy line represents a cis or trans configuration.] (However, (E, Z, Z) -2,4,7-tridecatrie 10 ⁻³ ppb as an unsaturated aldehyde of the formula (1), wherein the taste enhancer of a food or drink comprising an unsaturated aldehyde represented by (Nar and (Z, Z) -4,7-tridecadienal) -10 ⁴ ppb is added, The taste enhancement method of the food-drinks characterized by the above-mentioned. A method for enhancing the taste of a food or drink, comprising adding 10 ⁻³ ppb to 10 ⁴ ppb of the taste enhancer composition of the food or drink according to claim 6 as an unsaturated aldehyde of the formula (1). Following formula ( 3 )

[In the formula, ... Represents a single bond or a double bond, and a wavy line represents a cis or trans configuration.] (However, (E, Z, Z) -2,4,7-tridecatrie Noodles , except for (E, E, Z) -2,4,7-tridecatrienal and (Z , Z) -4,7-tridecadienal ) Agent. Following formula (1)

[In the formula,... Represents a single bond or a double bond, and a wavy line represents a cis or trans configuration.] (Where (E, Z, Z) -2,4,7-tridecatrienal A fish-flavoring agent comprising a unsaturated aldehyde represented by (E, E, Z) -2,4,7-tridecatrienal and (Z , Z) -4,7-tridecadienal ) A fish fragrance composition comprising 10 ⁻² ppm to 10 ⁴ ppm of an unsaturated aldehyde concentration of formula (1).
The food / beverage products which contain 10 < ^-3 > ppb-10 < ⁴ > ppb as the unsaturated aldehyde density | concentration of Formula (1) of the fish fragrance | flavor composition of Claim 10.

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