Flavoring ingredients containing ethyl-4,8-decadienoate

Abstract

A flavor composition is provided. The flavor composition comprises one or more decadienoate compounds and one or more flavor components. The one or more decadienoate compounds are selected from the group consisting of ethyl (4E,8E)decadienoate, ethyl (4Z,8E)decadienoate, ethyl (4E,8Z)decadienoate, ethyl (4Z,8Z)decadienoate and combinations thereof.

Description

[Technical Field]

[0001] Technical field This disclosure relates to flavor components and methods for producing them. More specifically, this disclosure relates to flavor compositions and beer-type beverages containing flavor components. Even more specifically, this disclosure relates to the use of flavor components to impart the natural fruity, pear-like characteristics of hops to beer-type beverages. [Background technology]

[0002] background Hops are a crucial component in beer flavor. The traditional method of brewing beer involves mixing malt and water (and, if necessary, other ingredients such as starchy grains) to obtain wort, allowing enzymes present in the malt (mainly amylase and protease) to act on it at approximately 40°C to 75°C to break down the malt starch into sugars, and then filtering. Hops are added to impart the characteristic aroma and bitterness of beer, the malt enzymes are stopped by boiling, the mixture is filtered, cooled further, yeast is added, yeast fermentation takes place at low temperatures to produce alcohol and alter the flavor, the yeast is removed by filtering, and then the mixture is aged at low temperatures.

[0003] With the diversification of consumer preferences in recent years, there has been a growing demand for the development of low-alcohol or non-alcoholic beer-type beverages with a variety of aromas and flavors. Non-alcoholic beer-flavored beverages have long been produced using de-alcoholization methods such as vacuum distillation, but recently developed products mainly consist of blends of bittering agents, body-enhancing agents, sweetening agents, souring agents, hop extracts, hop flavors, and carbon dioxide. However, because the hop extract components are not matured for a long period with this blend, the beer flavor is still insufficient compared to the natural hops found in beer. [Overview of the project]

[0004] Therefore, there remains a need for flavor components that are natural, mild, and strong, and that enable the imparting of hop flavor by adding them to the blending process of beer-type beverages, particularly non-alcoholic beer-type beverages, or to the post-fermentation or maturation process of beer-type alcoholic beverages.

[0005] Overview of Exemplary Embodiments In one exemplary embodiment, the flavor composition comprises one or more decadienoate ester compounds selected from the group consisting of ethyl (4E,8E) decadienoate, ethyl (4Z,8E) decadienoate, ethyl (4E,8Z) decadienoate, ethyl (4Z,8Z) decadienoate and combinations thereof; and one or more further flavor components.

[0006] In another exemplary embodiment, the beer-type beverage comprises one or more decadienoate ester compounds selected from the group consisting of ethyl(4E,8E)decadienoate, ethyl(4Z,8E)decadienoate, ethyl(4E,8Z)decadienoate, ethyl(4Z,8Z)decadienoate and combinations thereof; and a product base.

[0007] In yet another exemplary embodiment, the use of one or more decadienate ester compounds selected from the group consisting of ethyl(4E,8E)decadienate, ethyl(4Z,8E)decadienate, ethyl(4E,8Z)decadienate, ethyl(4Z,8Z)decadienate and combinations thereof is provided as an ingredient for imparting, enhancing, improving, or altering the hop flavor of a beer-type beverage.

[0008] Other features, aspects, and advantages of specific embodiments will become apparent to those skilled in the art upon reading this specification. [Modes for carrying out the invention]

[0009] Detailed description of exemplary embodiments The following text provides a broad description of numerous different embodiments of this disclosure. The description is to be interpreted as illustrative only and does not describe all possible embodiments, as it would be impractical, if not impossible, to describe all possible embodiments. Any feature, characteristic, component, composition, ingredient, product, process, or methodology described herein can be deleted in whole or in part, or combined with or replaced by any other feature, characteristic, component, composition, ingredient, product, process, or methodology described herein. Numerous alternative embodiments can be implemented using either the current art or art developed after the filing date of this patent, and these remain within the scope of the claims. All publications and patents cited herein are incorporated herein by reference.

[0010] This disclosure relates to the surprising finding that certain isomers of decadienate ester exhibit a more potent "fruity pear" character, and that using these specific isomers as flavoring ingredients makes it possible to create a more authentic hop flavor. In particular, this disclosure relates to the surprising finding that the flavoring components described herein can be used to provide beer-type beverages with an improved hop flavor and taste profile compared to typical beers.

[0011] In one embodiment, the flavor components of this disclosure may be added to flavor compositions for use in consumer goods. Generally, consumer goods include, but are not limited to, all kinds of foods, confectionery products, baked goods, sweets, savory products, fermented products, dairy products, non-dairy products, beverages, nutraceuticals, and pharmaceuticals.

[0012] As used herein, the term “beverage” means a drinkable composition. Beverages include, but are not limited to, water, carbonated water, flavored water, carbonated flavored water, milk derived from animals, soy, rice, coconut and other plant-based milk products, sports drinks, vitamin-fortified sports drinks, high-electrolyte sports drinks, high-caffeine high-energy drinks, coffee, decaffeinated coffee, tea, fruit-derived tea, herbal-derived tea, decaffeinated tea, wine, champagne, malt wine, rum, gin, vodka and other spirits, beer, low-calorie beer-type beverages, non-alcoholic beer and other beer-type beverages.

[0013] As used herein, the term “beer-type beverage” means an alcoholic or non-alcoholic carbonated beverage having a beer-like flavor. Therefore, “beer-type beverage” encompasses not only beer, which is a malt-fermented beverage obtained by fermenting malt, hops, and water using yeast, but also carbonated beverages having a beer flavor. That is, unless otherwise specified, a beer-type beverage in one aspect of this disclosure may be a fermented beer-type beverage that has undergone a fermentation process using yeast, or a non-fermented beer-type beverage that has not undergone a fermentation process. Furthermore, a beer-type beverage in one aspect of this disclosure may be an alcoholic beer-type beverage with an alcohol content of 1(v / v)% or more, or a non-alcoholic beer-type beverage with an alcohol content of less than 1(v / v)%. Non-alcoholic or alcohol-free beer-type beverages may be non-alcoholic fermented beer-type beverages produced by removing alcohol produced during the fermentation process after the fermentation process, or non-alcoholic unfermented beer-type beverages prepared to have a beer-like flavor without undergoing a fermentation process, or non-alcoholic or low-alcohol beverages produced by a fermentation process using yeast that produces little to no alcohol, or beverages produced by any combination of the above methods.

[0014] The general manufacturing process for non-alcoholic beer-type beverages is described below. Without the yeast fermentation process, non-alcoholic beer-type beverages can be easily manufactured. Common non-fermented non-alcoholic beer-type beverages include those made using malt as an ingredient and those made without malt.

[0015] In the production of non-alcoholic beer-type beverages using malt as a raw material, a mixture containing water and raw materials such as grains (e.g., malted grains), other grains, starch, sugars, bittering agents, or coloring agents as needed is mixed with enzymes such as amylase as needed. The resulting mixture is gelatinized, saccharified, and filtered to obtain a saccharified solution. The saccharified solution is mixed with hops, bittering agents, etc. as needed, then boiled, and subsequently solids such as coagulated proteins are removed in a clarification tank. The saccharified solution may be replaced with a boiled mixture of malt extract, hot water, and hops. Hops may be added to the mixture at any stage from the start to the end of boiling. The conditions for saccharification, boiling, and solid removal may be known conditions. After boiling, the resulting wort is filtered, and the filtrate is mixed with carbon dioxide gas. The resulting mixture is then packed into containers and sterilized to obtain the desired non-alcoholic beer-type beverage. When the decadienate ester according to this disclosure is added to this type of non-alcoholic beer-type beverage, the decadienate ester may be added at any point in the process, for example, after the wort has cooled, before or after filtration.

[0016] In the production of a non-alcoholic beer-type beverage that does not use malt as a raw material, liquid sugar containing a carbon source, a nitrogen source as an amino acid-containing substance other than grains and malt, hops, a coloring agent, etc. are mixed with warm water to obtain a liquid sugar solution. The liquid sugar solution is boiled. When using hops as a raw material, the hops can be mixed into the liquid sugar solution during boiling rather than before the start of boiling. The boiled liquid sugar solution is mixed with carbon dioxide gas. Then, the obtained mixture is packed into a container and sterilized to obtain the desired non-alcoholic beer-type beverage. When the decadienoic acid ester according to the present disclosure is added to this type of non-alcoholic beer-type beverage, the decadienoic acid ester may be added at any point during the process, for example, after the wort is cooled, either before or after filtration.

[0017] According to the present disclosure, when the decadienoic acid esters according to the following formulas (I, II, III, and IV) are used as flavor components in a flavor composition, they give more authentic hop characteristics and a strong fruity pear note.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0018] The flavor compositions according to this disclosure may have any preferred form, for example, as a liquid or solid, wet or dry, encapsulated in a carrier / particle or coated thereon, or as a powder. In a typical embodiment, one or more decadienate compounds present in the flavor composition may be at a concentration of about 10 ppb to about 100,000 ppm, and such flavor composition will be added to a beverage in an amount ranging from about 0.01% to about 1% such that the final concentration in the beverage is about 0.1 ppb to about 10 ppm.

[0019] In another embodiment, the amount of one or more decadienoate compounds that can be added to the consumable material may vary within a wide range and, in particular, depend on the properties of the consumable material or additive and the specific desired effect. Determining a suitable amount of one or more decadienoate compounds to be incorporated into the consumable material, depending on the end use and the desired effect, is well within the reach of those skilled in the art. In one embodiment, the amount of one or more decadienoate compounds present in the consumable material may be at a concentration of at least about 0.1 ppb to about 10 ppm. In another embodiment, the amount of one or more decadienoate compounds in the consumable material may be at a concentration of about 1 ppb to about 100 ppb.

[0020] In one embodiment, the amount of one or more decadienate ester compounds may be present in a beer-type beverage at a concentration of about 0.1 ppb to about 100 ppb; in another embodiment, it may be about 0.1 ppb to about 10 ppb; and in yet another embodiment, it may be about 1 ppb to about 10 ppb.

[0021] The decadienoate ester compounds according to this disclosure and formulas (I-IV) can be obtained using simple synthetic procedures and readily available starting materials known to those skilled in the art. In particular, the 4Z isomer can be synthesized, for example, by utilizing the Wittig reaction between a suitable 4-hexenal and (4-ethoxy-4-oxobutyl)(triphenyl)phosphonium bromide, using potassium tert-butoxide as a base. A similar synthesis method for methyl(4Z,8Z)-4,8-decadienoate has been reported by Marcuccio, SM et al. WO 01 / 46115. The 4E isomer can be synthesized by utilizing the Johnson-Claisen rearrangement using a appropriately derivatized allyl alcohol and triethyl orthoacetate.

[0022] The flavor compositions according to this disclosure may also contain further flavor components. Other further flavor components that can be used to provide flavor compositions, other than the decadienate ester compounds according to this disclosure and formulas (I-IV), may be selected from natural flavors, artificial flavors, spices, seasonings, etc., and synthetic flavor oils and flavor aromatics and / or oils, oleopolymers, essences, distillates, and extracts derived from plants, leaves, flowers, fruits, etc.

[0023] Flavoring oils include spearmint oil, cinnamon oil, wintergreen oil (methyl salicylate), peppermint oil, mint oil, clove oil, bay oil, hop oil, anise oil, eucalyptus oil, thyme oil, thuja oil, nutmeg oil, allspice, sage oil, mace, bitter almond oil, and cassia oil; useful flavoring agents include vanilla and citrus oils such as lemon, orange, lime, grapefruit, yuzu, and sudachi, as well as artificial, natural, and synthetic fruit flavors such as fruit essences including apple, pear, peach, grape, raspberry, blackberry, currant, blueberry, strawberry, cherry, plum, prune, raisin, cola, guarana, neroli, pineapple, apricot, banana, melon, tropical fruit, mango, mangosteen, pomegranate, and papaya, and combinations thereof.

[0024] Additional example flavors imparted by flavor-generating ingredients include: milk flavor, butter flavor, cheese flavor, hop flavor, cream flavor, and yogurt flavor; vanilla flavor, green tea flavor, oolong tea flavor, tea flavor, cocoa flavor, chocolate flavor, and coffee flavor; mint flavor, such as peppermint flavor, spearmint flavor, and mint flavor; agi flavor, ajwain flavor, anise flavor, angelica flavor, fennel flavor, allspice flavor, cinnamon flavor, chamomile flavor, mustard flavor, cardamom flavor, caraway flavor, cumin flavor, clove flavor, pepper flavor, coriander flavor, sassafras flavor, savory flavor, and zanthoxyli Spicy flavors such as fructus, perilla, juniper berry, ginger, star anise, horseradish, thyme, tarragon, dill, chili pepper, nutmeg, basil, marjoram, rosemary, bay leaf, and wasabi (Japanese horseradish); nut flavors such as almond, hazelnut, macadamia nut, peanut, pecan, pistachio, and walnut; floral flavors; and vegetable flavors such as onion, garlic, cabbage, carrot, celery, mushroom, and tomato.

[0025] In general, any flavoring ingredients or food additives can be used, as listed in "Chemicals Used in Food Processing," publication number 1274, pages 63-258, by the National Academy of Sciences.

[0026] Consumer materials may include product bases. As used herein, the term “product base” refers to all components necessary for a consumer material, apart from one or more decadienate compounds. These will naturally vary in both properties and proportions depending on the properties and applications of the consumer material or additive, but they are all well known in the art and can be used in proportions recognized in the art. Thus, formulations of such bases for all conceivable purposes are within the realm of the ordinary art.

[0027] Without limitation, and merely as examples, suitable bases may include anticaking agents, defoaming agents, antioxidants, binders, colorants, diluents, disintegrants, emulsifiers, encapsulating agents or encapsulated formulations, enzymes, oils and fats, flavor enhancers, flavor imparters, gums, polysaccharides, preservatives, proteins, solubilizers, solvents, stabilizers, sugar derivatives, surfactants, sweeteners, vitamins, waxes, etc. Solvents that can be used are known to those skilled in the art and include, for example, water, ethanol, ethylene glycol, propylene glycol, glycerin, and triacetin. Encapsulating agents and gums include maltodextrin, gum arabic, alginates, gelatin, modified starch, other polysaccharides, and proteins.

[0028] This disclosure is further described with reference to the following non-limiting examples.

[0029] example The following examples are given solely for illustrative purposes, as many variations of the invention are feasible without departing from the spirit and scope of this disclosure, and should not be construed as limitations of the invention. Example 1: Synthesis of ethyl (4E,8E)decadienoate (I) [ka]

[0030] (E)-N-methoxy-N-methylhexa-4-enamide(1):

[0031] (E)-Hexa-4-enoic acid (4.50 g, 1 equivalent, 39.4 mmol) was dissolved in THF (100 mL). N-methylmorpholine (12.0 g, 13.0 mL, 3 equivalents, 118 mmol) was added and the mixture was stirred for 5 minutes. 2-Chloro-4,6-dimethoxy-1,3,5-triazine (8.31 g, 1.2 equivalents, 47.3 mmol) was added in three portions over 10 minutes. The solution became slightly warm and a white precipitate formed. The mixture was stirred at room temperature for 90 minutes, then o,n-dimethylhydroxylamine HCl (3.85 g, 1 equivalent, 39.4 mmol) was added in two portions, and the mixture was stirred overnight at ambient temperature for 16 hours. The reaction was quenched with 100 ml of water. Note that not all precipitates dissolve in the solution. Extraction of the aqueous solution with 3 × 50 ml of MTBE was performed, and the organic matter was combined. Washing was performed with 2 × 50 ml of saturated potassium bicarbonate solution, 50 ml of 3 × 1 M HCl, and brine. Drying was performed on sodium sulfate, and the solvent was removed under vacuum. The desired product was purified by silica gel column chromatography using a hexane-ethyl acetate gradient. 2.7 g (44%) of clear oil (1) was isolated.

[0032] 1 H NMR (300 MHz, CDCl3) δ = 1.65 (d, J=4.2 Hz, 3H), 2.34 - 2.27 (m, 2H), 2.48 (t, J=7.2 Hz, 2H) 3.18 (s, 3H), 3.68 (s, 3H), 5.54 - 5.41 (m, 2H). 13 C NMR (125 MHz, CDCl3) δ = 17.84, 27.51, 32.15 ,61.17, 125.72, 129.94, 174.12.

[0033] (E)-Octa-1,6-diene-3-one(2):

[0034] (E)-N-methoxy-N-methylhexa-4-enamide (2.70 g, 1 equivalent, 17.2 mmol) was dissolved in THF (50 mL) and cooled to -20°C in an isopropyl alcohol / dry ice bath. Chloro(vinyl)magnesium (1.79 g, 10.3 mL, 2 mol, 1.2 equivalents, 20.6 mmol) (purchased from Acros, newly opened bottle) was added dropwise and stirred. The reaction was heated to ambient temperature for 1 hour, and then stirred at ambient temperature for another hour. The reaction was cooled in an ice bath and quenched with saturated ammonium chloride. Diluted with water and MTBE. The organic layer was separated and extracted with 3 × MTBE in aqueous solution. The organic matter was combined and washed with 1 × brine. The organic layer was collected and dried on sodium sulfate. 1.75 g (82%) of clear oil (2) was isolated.

[0035] 1 H NMR (300 MHz, CDCl3) δ = 1.64 (d, J=4.7 Hz, 3H), 2.34 - 2.27 (m, 2H), 2.64 (t, J=7.2 Hz, 2H), 5.53 - 5.37 (m, 2H), 5.82 (dd, J=10.3, 1.3 Hz, 1H), 6.21 (dd, J=17.4, 1.3 Hz, 1H), 6.35 (dd, J=17.4, 10.3, 1H). 13 C NMR (125 MHz, CDCl3) δ = 17.84, 26.84, 39.44, 125.91, 127.96, 129.54, 136.56, 200.3.

[0036] (E)-Octa-1,6-diene-3-ol(3):

[0037] Dissolve (E)-octa-1,6-dien-3-one (1.19 g, 1 equivalent, 9.58 mmol) in MeOH (30 mL). Add cerium(III) chloride heptahydrate (3.93 g, 1.1 equivalents, 10.5 mmol) and stir until dissolved at ambient temperature. Cool to -5°C in an isopropyl alcohol / dry ice bath. Add sodium borohydride (363 mg, 1 equivalent, 9.58 mmol) in three portions and stir for 20 minutes. Quench with saturated ammonium chloride solution (100 ml) and extract with 5 × 50 ml MTBE. Combine organic matter and wash with brine. Dry on sodium sulfate and isolate 1.15 g of clear oil (3) by passing through a silica gel column using a pentane-MTBE gradient.

[0038] 1 H NMR (300 MHz, CDCl3) δ = 1.66 - 1.54 (m, 5H), 2.11 - 2.04 (m, 2H), 4.14 - 4.08 (m,1H), 5.10 (d, J=10.5 Hz, 1H), 5.22 (d, J=17.1 Hz, 1H), 5.51 - 5.43 (m, 2H), 5.86 (ddd, J=17.1, 10.5, 6.1, 1H) 13 C NMR (125 MHz, CDCl3) δ = 17.91, 28.48, 36.7, 72.82, 114.57, 125.49, 130.68, 141.13.

[0039] Ethyl (4E,8E) decadienate (I):

[0040] Triethyl orthoacetate (1.25 g, 1.42 mL, 1.95 equivalents, 7.73 mmol), (E)-octa-1,6-dien-3-ol (0.500 g, 1 equivalent, 3.96 mmol), and propionic acid (14.7 mg, 14.8 μL, 0.05 equivalents, 198 μmol) were added to a microwave vial, flushed with argon, and sealed with a cap. The mixture was heated in an oil bath at 100°C for 2 hours, then heated to 140°C for 3 hours. The reaction was cooled and diluted with a mixture of pentane and MTBE. The organic layer was washed with 2 × 1 M HCl, 1 × saturated sodium bicarbonate, and 1 × brine. The mixture was dried over sodium sulfate. The mixture was traced on a silica gel column using a 98:2 pentane-MTBE gradient. 520 mg of clear oil (66%) was isolated.

[0041] 1 H NMR (300 MHz, CDCl3) δ = 1.25 (t, J=7.1 Hz, 3H), 1.64 - 1.63 (m, 3H), 2.07 - 1.99 (m, 4H), 2.39 - 2.26 (m, 4H), 4.12 (q, J=7.1, 2H), 5.52 - 5.34 (m, 4H). 13 C NMR (125 MHz, CDCl3) δ = 14.26, 17.91, 27.94, 32.53, 32.57, 34.41, 60.23, 125.07, 128.3, 130.77, 131.16, 173.27. Example 2: Synthesis of ethyl(4Z,8E)decadienoate(II) [ka]

[0042] Ethyl (4Z,8E)decadinoate (II):

[0043] Ethyl 4-(bromotriphenyl-l5-phosphanyl)butanoate (4.17 g, 1.2 eq, 9.11 mmol) was pulverized into a powder, added to a 200 ml round-bottom flask, and THF (35 mL) was added to the flask. It was cooled in an ice bath, and potassium tert-butoxide (1.02 g, 1.2 eq, 9.11 mmol) was added in three portions. Stir for 30 minutes in an ice bath and then for 30 minutes at ambient temperature. The reaction turns orange. Cool again in an ice bath and add a precooled solution of freshly prepared (E)-hex-4-enal (0.745 g, 1 eq, 7.59 mmol) via a cannula. Stir the reaction for 30 minutes and then bring to ambient temperature for 2.5 hours. Monitor the reaction by TLC and GC-MS. Cool the reaction in an ice bath and quench with saturated ammonium chloride solution. Dilute with ammonium chloride solution and a 50:50 pentane-MTBE mixture (100 ml). Recover the organic matter and wash with brine. Dry over sodium sulfate. Remove the solvent in vacuo. Purify by silica gel column using 50:50 hexane-CH2Cl2 to remove triphenylphosphine oxide. The isolated material was run on a second column using a gradient from 99.5 pentane - 0.5 MTBE to 98:2 pentane - MTBE. The pure fractions were collected and the solvent was removed in vacuo to give 0.450 grams (30%) of a clear oil (II).

[0044] 1 H NMR (300 MHz, CDCl3) δ = 1.25 (t, J=7.1 Hz, 3H), 1.65 - 1.63 (m, 3H), 2.14 - 1.99 (m, 4H), 2.38 - 2.31 (m, 4H), 4.11 (q, J=7.1, 2H), 5.47 - 5.30 (m, 4H). 13 C NMR (125 MHz, CDCl3) δ = 14.25, 17.91, 22.88, 27.27, 32.54, 34.39, 60.3, 125.24, 127.71, 130.76, 173.26. Example 3: Synthesis of ethyl (4E,8Z) decadienoate (III) [ka]

[0045] (Z)-N-methoxy-N-methylhexa-4-enamide(6):

[0046] (Z)-Hexa-4-enoic acid (2.00 g, 1 equivalent, 17.5 mmol) was dissolved in dichloromethane (80 mL) and cooled in an ice bath. Triethylamine (5.32 g, 7.33 mL, 3 equivalents, 52.6 mmol) was slowly added by syringe, followed by o,n-dimethyl-hydroxyamine HCl (1.71 g, 1 equivalent, 17.5 mmol) in two batches. The mixture was stirred for 10 minutes, and then 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI) (3.36 g, 1 equivalent, 17.5 mmol) was added in three batches over 10 minutes. The reaction was stirred, and the ice bath was allowed to cool to room temperature. The mixture was stirred overnight for 20 hours. A large amount of white precipitate was formed. The reaction was diluted with 100 ml of water and partitioned using a separation funnel. Extraction of the aqueous solution was performed using 3 × 30 ml of DCM. The organic matter is combined and washed with 2 x 100 ml of 1 M HCl, 50 ml of 2 x saturated sodium bicarbonate, and 1 x 50 ml of brine. It is dried on sodium sulfate. It is purified by silica gel column chromatography. 1.6 g (58%) of clear oil (6) is recovered.

[0047] 1 H NMR (300 MHz, CDCl3) δ = 1.64 (d, J=6.2 Hz, 3H), 2.41 - 2.34 (m, 2H), 2.51 - 2.48 (m, 2H), 3.18 (s, 3H), 3.68 (s, 3H), 5.54 - 5.36 (m, 2H). 13 C NMR (125 MHz, CDCl3) δ = 12.71, 22.08, 31.79, 61.19, 124.99, 129.03, 174.1.

[0048] (Z)-Octa-1,6-diene-3-one(7):

[0049] (Z)-N-methoxy-N-methylhexa-4-enamide (1.60 g, 1 equivalent, 10.2 mmol) was dissolved in THF (50 mL) and cooled to -20°C in an isopropyl alcohol / dry ice bath. Chloro(vinyl)magnesium (1.06 g, 6.11 mL, 2 mol, 1.2 equivalents, 12.2 mmol) (purchased from Acros, newly opened bottle) was added dropwise and stirred. The reaction was warmed to ambient temperature over 1 hour. Stirring was continued for another 60 minutes. The reaction was cooled in an ice bath and quenched with saturated ammonium chloride. Diluted with water and MTBE. The organic layer was separated and washed with 3 × MTBE aqueous solution. The organic matter was combined and washed with 1 × brine. The organic layer was collected and dried on sodium sulfate. Purified by silica gel column. 647 mg, 51% clear oil (7) was isolated.

[0050] 1 H NMR (300 MHz, CDCl3) δ = 1.63 (d, J=7.2 Hz, 3H),2.40 - 2.33 (m, 2H), 2.65 (t, J=7.3, 2H), 5.41 - 5.32 (m, 1H), 5.54 - 5.42 (m, 1H), 5.83 (dd, J=10.3, 1.3, 1H), 6.22 (dd, J=17.6, 1.3, 1H), 6.36 (d,d, J=17.6, 10.3, 1H). 13 C NMR (125 MHz, CDCl3) δ = 12.7, 21.4, 39.31, 125.1, 128, 128.67, 136.54, 200.31.

[0051] (Z)-Octa-1,6-diene-3-ol(8):

[0052] (Z)-Octa-1,6-dien-3-one (0.647 g, 1 equivalent, 5.21 mmol) was dissolved in MeOH (25 mL). Cerium(III) chloride heptahydrate (2.14 g, 1.1 equivalent, 5.73 mmol) was added and stirred until dissolved at room temperature. The mixture was cooled to -5°C in an isopropyl alcohol / dry ice bath. Sodium borohydride (197 mg, 1 equivalent, 5.21 mmol) was added in three portions and stirred for 30 minutes. The mixture was quenched with saturated ammonium chloride solution (100 ml) and extracted with 5 × 50 ml of MTBE. The organic matter was combined and washed with brine. The mixture was dried on sodium sulfate and analyzed on a silica gel column with 95:5 pentane-MTBE to 90:10 pentane-MTBE. 0.601 g (91%) of clear oil (8) was isolated.

[0053] 1 H NMR (300 MHz, CDCl3) δ = 1.65 - 1.56 (m, 5H), 2.18 - 2.11 (m, 2H), 4.16 - 4.09 (m, 1H), 5.11 (d, J=10.2, 1H), 5.23 (d, J=16.7, 1H), 5.51 - 5.36 (m, 2H), 5.88 (ddd, J=6, 10.2, 16.7). 13 C NMR (125 MHz, CDCl3) δ = 12.78, 22.84, 36.68, 114.68, 124.56, 129.85, 141.12.

[0054] Ethyl (4E,8Z) Decadienate (III):

[0055] (Z)-Octa-1,6-dien-3-ol (0.550 g, 1 equivalent, 4.36 mmol) was dissolved in a microwave vial with triethyl orthoacetate (4.95 g, 5.59 mL, 7 equivalents, 30.5 mmol), and propionic acid (12.9 mg, 13.0 μL, 0.04 equivalents, 174 μmol) was added. The vial was capped and heated to 100°C for 3 hours. The reaction was then heated to 140°C for 2.5 hours. The reaction was cooled and diluted with 100 ml of 50:50 pentane-MTBE. The organic layer was washed with 2 × 1 M HCl, 1 × saturated sodium bicarbonate solution, and 1 × brine. The organic matter was collected and dried on sodium sulfate. It was purified by slicing on a silica column using a 100% pentane ~ 98:2 pentane-MTBE gradient. 473 mg of III is isolated as a clear oil.

[0056] 1 H NMR (300 MHz, CDCl3) δ = 1.25 (t, J=7.1 Hz, 3H), 1.59 (d, J=5.9, 3H), 2.09 - 2.02 (m, 4H), 2.39 - 2.27 (m, 4H), 4.12 (q, J=7.1, 2H), 5.53 - 5.32 (m, 4H). 13 C NMR (125 MHz, CDCl3) δ = 12.81, 14.27, 26.8, 27.94, 32.4, 34.39, 60.24, 124.09, 128.39, 129.91, 131.13, 173.26. Example 4: Synthesis of ethyl(4Z,8Z)decadienoate(IV) [ka]

[0057] Ethyl (4Z,8Z) Decadienate (IV):

[0058] Ethyl 4-(bromotriphenyl-15-phosphanail)butanoate (5.59 g, 1.2 equivalents, 12.2 mmol) was ground into a powder and added to a 200 ml round-bottom flask, and THF (40 mL) was added to the flask. The reaction was cooled in an ice bath, and potassium tert-butoxide (1.37 g, 1.2 equivalents, 12.2 mmol) was added in three portions. The mixture was stirred in an ice bath for 30 minutes, then at ambient temperature for 30 minutes. The reaction turned orange. The mixture was cooled again in an ice bath, and a hexane-DCM pre-cooled solution of (Z)-hexa-4-enal (1.00 g, 1 equivalent, 10.2 mmol) was added via a cannula. The mixture was stirred in an ice bath for 30 minutes, then at room temperature for 2.5 hours. The reaction was quenched with saturated ammonium chloride solution after 4 hours. The aqueous phase was extracted with 1 × MTBE. The organic matter was combined and washed with brine. The organic matter was recovered. The oil was obtained by drying on sodium sulfate and removing the solvent in a vacuum. Some solid precipitated. The product was dissolved in a small amount of dichloromethane and diluted in a 50:50 mixture with hexane. Triphenylphosphine oxide was removed by purification using a silica gel column with a 50:50 CH2Cl2-hexane solvent system. A second silica gel column was used with a pentane-MTBE gradient of 100% pentane ~ 98:2 pentane-MTBE. By fractionation, 0.9 grams of pure IV was obtained as a clear oil.

[0059] 1 H NMR (300 MHz, CDCl3) δ = 1.26 (t, J=7.1, 3H), 1.61 (d, J=5.9, 3H), 2.15 - 2.04 (m, 4H), 2.40 - 2.30 (m, 4H),4.13 (q, J=7.1, 2H), 5.49 - 5.32 (m, 4H). 13 C NMR (125 MHz, CDCl3) δ = 12.81, 14.26, 22.87, 26.85, 27.14, 34.41, 60.31, 124.31, 127.86, 129.91, 130.77, 173.25.

[0060] Next, decadienate ester compounds (I-IV) were tested in the blended model beer base, and their additional effects on the aroma and taste of the model beer (base + ester) were compared with the control (base without ester) and are shown in Table I. Table I [Table 1]

[0061] When expressed in "ppm," the concentration is, depending on the context, one part per million of the total weight of the consumable or additive. Where a range of values ​​is stated in this disclosure, it should be understood that all possible values ​​within that range, including the endpoint, are to be considered disclosed. For example, the "range of 1 ppm to 1000 ppm" for roasted barley flavor modifier extract should be read as indicating each and all possible numbers along the continuum between 1 and 1000. It should be understood that the inventors recognize and understand that all possible values ​​within the range should be considered specified, and that the inventors have the entire range and all values ​​within that range at their disposal.

[0062] In this disclosure, the term “about” as used in relation to a value is inclusive of the stated value and has a meaning determined by the context. For example, it includes at least the degree of error associated with measuring a particular value. Those skilled in the art will understand that in this specification, the term “about” means that an amount “about” of the stated value produces the desired degree of effect in the composition and / or method of this disclosure. Those skilled in the art will further understand that the boundary of the “about” range with respect to the proportion, amount, or quantity of any component in an embodiment can be determined by varying the value, determining the effect of the composition or method for each value, and determining the range of values ​​that produce a composition or method that produces the desired degree of effect according to this disclosure.

[0063] While specific embodiments of the present invention have been illustrated and described, those skilled in the art will understand that various changes and modifications are possible without departing from the spirit and scope of the invention. Accordingly, the appended claims are intended to encompass all changes and modifications that fall within the scope of the present invention.

Claims

1. One or more decadienoate ester compounds selected from the group consisting of ethyl(4E,8E)decadienoate, ethyl(4Z,8E)decadienoate, ethyl(4E,8Z)decadienoate, ethyl(4Z,8Z)decadienoate and combinations thereof; and 1 or more additional flavor ingredients A flavor composition containing the following:

2. The flavor composition according to claim 1, comprising one or more decadienate ester compounds in a concentration of 10 ppb to 100,000 ppm.

3. The flavor composition according to claim 1, comprising one or more decadienate ester compounds in a concentration of 100 ppb to 10,000 ppm.

4. A consumer product comprising the flavor composition described in claim 1.

5. The consumer product according to claim 4, wherein the consumer product is a beverage.

6. The consumer product according to claim 5, wherein the beverage is a beer-type beverage.

7. One or more decadienoate ester compounds selected from the group consisting of ethyl(4E,8E)decadienoate, ethyl(4Z,8E)decadienoate, ethyl(4E,8Z)decadienoate, ethyl(4Z,8Z)decadienoate and combinations thereof; and Product-based A beer-type beverage that includes [this ingredient].

8. The beverage according to claim 7, wherein the beverage has an alcohol content of less than 1.0%.

9. The beverage according to claim 8, wherein the beverage is an alcohol-free beer-type beverage.

10. The beverage according to claim 7, wherein the beverage has an alcohol content of more than 1.0%.

11. The beverage according to claim 10, wherein the beverage is an alcohol-containing beer-type beverage.

12. Use of one or more decadienate ester compounds selected from the group consisting of ethyl(4E,8E)decadienate, ethyl(4Z,8E)decadienate, ethyl(4E,8Z)decadienate, ethyl(4Z,8Z)decadienate and combinations thereof, as an ingredient to impart, enhance, improve, or alter the hop flavor of beer-type beverages.

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