Improvements in or relating to organic compounds

Abstract

1. Use of a compound according to formula (I), having X, Y = -NH- or -O-, wherein at least X or Y is -NH-, in the form of any one of its stereoisomers, or a mixture thereof, wherein denotes a carbon-carbon single or double bond, one carbon-carbon double bond being present at either C2 or C3, and the wavy bond denotes an unspecified arrangement of adjacent double bonds, as an umami tastant.

Description

[Technical Field]

[0001] The present invention is directed to umami flavors and methods of making same. It relates to compounds that provide umami sensation and savory flavors, and their use in compositions and consumable products. [Background technology]

[0002] Umami is a flavor sensation commonly associated with Asian cuisine. It is described as savory or meaty and is characteristic of broths and cooked meats. Furthermore, improved umami sensation can help make reduced-salt products more palatable. Umami flavor has traditionally been achieved by the addition of monosodium glutamate (MSG) to foods. However, some consumers believe that glutamates, particularly MSG, have adverse effects, and as a result, there remains a need for non-glutamate-based compounds that replace or reduce the reliance on such compounds to modify the umami sensation and savory flavor of consumable products.

[0003] Amides of cinnamic acid derivatives and aromatic amines from natural sources have been reported as natural or nature-identical umami tastants in US2012308703A1, WO2013000673A1, or WO2014083202A1. Flavor compositions containing such amides and additional substances are disclosed in WO2014095564A1. A specific class of cinnamides capable of producing a trigeminal effect is the subject of the recently published WO2019063069A1. Summary of the Invention

[0004] Surprisingly, it has now been found that certain putrescine bisamide and amide ester analogues, i.e., those of putrescine (butane-1,4-diamine) and 4-aminobutan-1-ol, having, for example, a cinnamic acid, cinnamic acid derivative, or 4-methoxybenzoic acid moiety on the one hand, and tiglic acid ((2E)-2-methylbut-2-enoic acid) on the other, can be used as umami tastants.

[0005] Thus, in a first aspect of the present invention, there is provided the use of certain putrescine bisamide and amide ester analogues as ingredients to impart, enhance, improve or modify the umami taste sensation of a consumable composition. Additionally, flavor compositions are provided that include a flavor ingredient and a putrescine bisamide or amide ester analog. Additionally, consumable compositions are provided having an umami flavor, said umami flavor being provided at least in part by the presence of certain putrescine bisamide or amide ester analogs.

[0006] In a further aspect of the present invention, novel putrescine bisamide and amide ester analogs are provided. In a first aspect of the present invention, a compound of formula (I) [ka] [ka] and X, Y=—NH— or —O—, where at least X or Y is —NH—, the use of one or more compounds according to the formula [ka] indicates a carbon-carbon single or double bond, with one carbon-carbon double bond being present at either C2 or C3; A wavy bond indicates an arbitrary arrangement of adjacent double bonds; Said use as an ingredient to impart, enhance, improve or modify the umami taste sensation of a consumable composition is provided.

[0007] In one embodiment of the present invention, a compound of formula (II) [ka] [ka] wherein the wavy bond indicates any arrangement of adjacent double bonds, as an ingredient to impart, enhance, improve or modify the umami taste sensation of a consumable composition.

[0008] Compounds according to formula (II) are bisamides and correspond to compounds according to formula (I), wherein X and Y are -NH-, and wherein one carbon-carbon double bond is at C2.

[0009] In a further aspect of the invention, there is provided the use of a compound according to formula (I) as defined above, wherein the compound is selected from the group consisting of (E)-N-(4-cinnamamidobutyl)-2-methylbut-2-enamide, (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamido)butyl)-2-methylbut-2-enamide, (E)-4-methoxy-N-(4-(2-methylbut-2-enamido)butyl)benzamide, 4-cinnamamidobutyl (E)-2-methylbut-2-enoate, 4-cinnamamidobutyl 2-methylbut-3-enoate and 4-((E)-2-methylbut-2-enamido)butylcinnamate.

[0010] In a further aspect of the present invention, there is provided the use of a mixture of compounds according to formula (I) as defined above. More specifically, there is provided the use of a mixture of 4-cinnamamidobutyl (E)-2-methylbut-2-enoate and 4-cinnamamidobutyl 2-methylbut-3-enoate in a ratio of 1:2.

[0011] In a further aspect of the present invention, there is provided the use of a compound according to formula (II) as defined above, wherein the compound is selected from the group consisting of (E)-N-(4-cinnamamidobutyl)-2-methylbut-2-enamide, (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamido)butyl)-2-methylbut-2-enamide and (E)-4-methoxy-N-(4-(2-methylbut-2-enamido)butyl)benzamide.

[0012] Further provided is an umami flavour composition comprising one or more compounds according to formula (I) or according to formula (II) and one or more further flavour ingredients. The compounds according to formula (I) or according to formula (II) can be used alone as the sole flavor component in a consumable composition or in combination with additional flavor components to provide a flavor composition ready to be added to the consumable composition. The additional flavor components may contain other umami tastants and / or umami sensation or flavor enhancers, including MSG. The use of compounds according to formula (I) or according to formula (II) allows for a significant reduction in MSG levels, and in some cases, allows for the complete elimination of MSG.

[0013] The other umami tastants and / or the umami sensation or flavor enhancers include, but are not limited to, L-Glu (glutamic acid, glutamate, e.g., in the form of its salts such as monosodium glutamate, potassium glutamate, ammonium glutamate, calcium glutamate, magnesium glutamate, etc.), L-Asp (L-asparagine, or a salt thereof), 5'-ribonucleotides or salts thereof, including, but not limited to, calcium 5'-ribonucleotides, disodium 5'-ribonucleotides, and dipotassium 5'-ribonucleotides (e.g., inosinic acid, guanylic acid, adenosinic acid, inosinate, guanylate, and adenosinate). Nilate salts, including guanosine 5'-monophosphate, inosine 5'-monophosphate, and 5'-adenylic acid and salts thereof, such as disodium guanylate, disodium inosinate, disodium adenylate, dipotassium guanylate, dipotassium inosinate, dipotassium adenylate, calcium guanylate, calcium inosinate, calcium adenylate, etc.), maltol, ethyl maltol, glycine, L-leucine, autolyzed or hydrolyzed proteins (e.g., autolyzed yeast, hydrolyzed yeast, hydrolyzed vegetable protein), Koji-Aji (a nucleotide-rich yeast extract having fermented wheat gluten and maltodextrin, also Ajinomoto Food Ingredients, LLC.), and natural preparations or extracts containing one or more of the above, such as extracts, purees or concentrates of vegetables (including mushrooms, shiitake, soy, tomato, potato, whey, kelp / seaweed), cereals, meat, fish (e.g., shellfish, masago), fresh or fermented, derived from related ingredients, milk in partially or fully hydrolyzed forms (e.g., various hydrolyzed proteins), cheese, and egg yolk.

[0014] Specific examples of said other umami tastants and / or said umami sensation or savory flavor enhancers include the compounds described in UK Patent Application No. 0913804 and International Application PCT / EP2010 / 059916. Other non-limiting examples of compounds that impart and enhance umami flavor include those described in EP 1642886, WO 2005 / 015158, EP 1312268, WO 2003 / 088768, EP1291342, and WO2006 / 003107, all of which are incorporated herein by reference.

[0015] In addition to other umami tastants and / or umami sensation or savory flavor enhancers, other additional flavor ingredients that may be used in combination with a compound according to Formula (I) or according to Formula (II) to provide a flavor composition may be selected from natural flavors, artificial flavors, spices, flavorings, etc., synthetic flavor oils and flavor aromas and / or oils, oleoresins, essences, distillates, and extracts derived from plants, leaves, flowers, fruits, and the like. Generally, any flavor or food additive may be used, such as those described in Chemicals Used in Food Processing, Publication 1274, pp. 63-258, by the National Academy of Sciences. This publication is incorporated herein by reference.

[0016] The compound according to formula (I) or according to formula (II) may be used directly in the consumable composition, or it may form part of a flavor composition, especially an umami flavor composition, which is subsequently mixed with the consumable composition. In specific embodiments, the compound according to formula (I) or according to formula (II) may be used in an amount of about 0.001 to 100% by weight, or 0.01 to 10% by weight, more preferably 0.1 to 10% by weight, and even more preferably 0.5 to 5% by weight, based on the flavor composition.

[0017] The compound according to formula (I) or according to formula (II) can further be used in a flavor composition in combination with one or more ingredients or excipients conventionally used in flavor compositions, such as carrier materials and other auxiliaries commonly used in the art. Suitable excipients for flavor compositions are well known in the art, and include, for example, but are not limited to, solvents (including water, alcohol, ethanol, oils, fats, vegetable oils, and miglyol), binders, diluents, disintegrants, lubricants, flavoring agents, coloring agents, preservatives, antioxidants, emulsifiers, stabilizers, flavor enhancers, anti-caking agents, etc.

[0018] Examples of such carriers or diluents for flavor compositions can be found, for example, in "Perfume and Flavor Materials of Natural Origin", S. Arctander, Ed., Elizabeth, NJ, 1960; "Perfume and Flavor Chemicals", S. Arctander, Ed., Vol. I & II, Allured Publishing Corporation, Carol Stream, USA, 1994; in "Flavorings", E. Ziegler and H. Ziegler (ed.), Wiley-VCH Weinheim, 1998, and "CTFA Cosmetic Ingredient Handbook", J.M. Nikitakis (ed.), 1st ed., The Cosmetic, Toiletry and Fragrance Association, Inc., Washington, 1988. Other suitable and desirable ingredients of flavor compositions are described in standard texts such as "Handbook of Industrial Chemical Additives", ed. M. and I. Ash, 2nd Ed., (Synapse 2000).

[0019] Additionally, consumable compositions are provided having an umami flavor, said umami flavor being provided at least in part by the presence therein of a compound according to formula (I) or according to formula (II). Further provided is a consumable composition comprising at least one compound according to Formula (I) or according to Formula (II), or one or more compounds according to Formula (I) or according to Formula (II); and an umami flavor composition comprising a product base.

[0020] The proportion of a compound according to Formula (I) or Formula (II) used in a consumable composition will depend on the nature of the use and the desired effect. For example, the proportion required for partial replacement of MSG will naturally be lower than for complete replacement. The proportion may vary between wide limits, typically between 0.01 ppm and 10,000 ppm by weight of the consumable composition, more specifically between 0.1 ppm and 1,000 ppm, and even more specifically between 1 ppm and 500 ppm or between 5 and 50 ppm. However, these are only general guidelines for useful proportions, and skilled flavorists may use proportions outside these ranges for specific effects.

[0021] "Consumable composition" means any composition that is taken into the mouth for eventual expectoration or ingestion. The composition can be in any physical form, solid, liquid, or gas. Non-limiting examples include all food products, food additives, dietary supplements, pharmaceuticals, and any product that is placed in the mouth, including (but not limited to) chewing gum, oral care products, and oral hygiene products, including but not limited to cereal products, rice products, tapioca products, sago products, baker's products, biscuit products, pastry products, bread products, confectionery products, dessert products, gum, chewing gum, flavored or flavored coated food / drink containers, yeast products, baking powder, salt and spice products, snack foods, savory products, mustard products, vinegar products, sauces (condiments), soups, seasonings, ready-to-eat meals, gravies, nuts & nut products, processed foods, vegetable products, meat and meat products, egg products, milk and dairy products, yogurt, cheese products, butter and butter substitutes, milk substitutes, Soy products, edible oil and fat products, beverages, carbonated beverages, alcoholic beverages such as beer, wine and spirits, non-alcoholic beverages such as soft drinks, or other flavored articles including forms requiring reconstitution, including, but not limited to, beverage powders, milk-based beverage powders, sugar-free beverage powders, beverage syrups, beverage concentrates, coffee and tea, food extracts, plant extracts, meat extracts, seasonings, gelatin, pharmaceutical and non-pharmaceutical gums, tablets, lozenges, drops, emulsions, elixirs, syrups and other formulations for making beverages, and combinations thereof.

[0022] In particular, the compounds according to formula (I) or according to formula (II) are suitable for consumable compositions selected from the group consisting of flavor applications, including snacks, soups, broths, sauces, meat / protein and ready-to-eat meals, among others. "Product base" means the combination of all conventional, art-recognized ingredients required for a particular consumable composition.

[0023] In a further aspect of the invention, there is provided a method of providing a consumable composition having an umami taste sensation, comprising the step of adding one or more compounds according to formula (I) or according to formula (II) to the consumable composition.

[0024] In a further embodiment of the present invention, a compound of formula (I) [ka] [ka] and X, Y=—NH— or —O—, where at least X or Y is —NH—, in the form of any one of its stereoisomers or a mixture thereof, [ka] indicates a carbon-carbon single or double bond, with one carbon-carbon double bond being present at either C2 or C3; The wavy bond indicates an unspecified arrangement of adjacent double bonds, provided that the compound is not (E)-N-(4-cinnamamidobutyl)-2-methylbut-2-enamide. is provided.

[0025] A new class of putrescine bisamides has been found in extracts of Aglaia gracilis (Inada et al., Phytochemistry 53, 2000, 1091-1095). Two of them have been identified as cinnamamides, including (E)-N-(4-cinnamamidobutyl)-2-methylbut-2-enamide. Their synthesis has been reported (Deterbeck et al., Tetrahedron, 58 (2002) 6887-6893).

[0026] In particular, the compound according to formula (I) is selected from the group consisting of (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamido)butyl)-2-methylbut-2-enamide, (E)-4-methoxy-N-(4-(2-methylbut-2-enamido)butyl)benzamide, 4-cinnamamidobutyl (E)-2-methylbut-2-enoate, 4-cinnamamidobutyl 2-methylbut-3-enoate and 4-((E)-2-methylbut-2-enamido)butylcinnamate.

[0027] Compounds according to formula (I) or formula (II) can be obtained using simple synthetic procedures and readily available starting materials known to those skilled in the art. Specific reaction conditions are further described in the examples. The present invention is further described by the following non-limiting examples that represent specific embodiments.

[0028] example: Example 1: Synthesis of (E)-N-(4-cinnamamidobutyl)-2-methylbut-2-enamide (Ia) [ka]

[0029] 1a) tert-Butyl (4-cinnamamidobutyl)carbamate (1): A solution of cinnamoyl chloride (4.21 g, 25.3 mmol) in dichloromethane (50 ml) was added dropwise to a solution of tert-butyl(4-aminobutyl)carbamate (5 g, 26.6 mmol) and triethylamine (3.07 g, 30.4 mmol) in dichloromethane (200 ml) cooled in an ice bath. After stirring at room temperature for 2 h, the reaction mixture was washed successively with 1 M HCl (2 × 100 ml), saturated NaHCO (100 ml), and HO (100 ml). The organic phase was dried over MgSO, filtered, and concentrated. The resulting solid was washed with MTBE / pentane and then dried in a vacuum oven at 40 °C. This yielded 7.5 g (93%) of tert-butyl(4-cinnamamidobutyl)carbamate (1) as a white powder. The purity is >95% by NMR analysis. 1H NMR (600 MHz, DMSO-d6) δ = 1.15 - 1.58 (m, 13 H), 2.82 - 3.00 (m, 2 H), 3.08 - 3.23 (m, 2 H), 6.55 - 6.70 (m, 1 H), 6.77 - 6.92 (m, 1 H), 7.29 - 7.47 (m, 4 H), 7.49 - 7.66 (m, 2 H), 8.03 - 8.32 (m, 1 H) ppm. 13C NMR (151 MHz, DMSO-d6) δ = 26.74, 27.26, 28.44, 38.61, 39.65, 77.52, 122.48, 127.63, 129.10, 129.54, 135.11, 138.55, 155.77, 164.96 ppm.

[0030] 1b) N-(4-aminobutyl)cinnamamide (2): TFA (4.84 ml, 62.8 mmol) was added to a solution of tert-butyl (4-cinnamamidobutyl)carbamate (1) (2 g, 6.28 mmol) in dichloromethane (100 ml). After stirring at room temperature for 2 hours, the volatiles were removed under reduced pressure (up to 20 mbar) at 50 °C. The intermediate N-(4-aminobutyl)cinnamamide (2, N-(4-aminobutyl)-3-phenyl-prop-2-enamide) was obtained as a viscous yellow oil, which was used in the following step 1c) without further purification.

[0031] 1c) (E)-N-(4-cinnamamidobutyl)-2-methylbut-2-enamide (Ia): The intermediate N-(4-aminobutyl)cinnamamide (2) was dissolved in dichloromethane. To the resulting solution, triethylamine (5.25 ml, 37.7 mmol) was added with stirring at room temperature. A solution of (E)-2-methylbut-2-enoyl chloride (1.043 g, 8.79 mmol) in dichloromethane (10 ml) was then added dropwise. Stirring was continued for 2 hours, and the solution was then left at room temperature overnight. The next day, the solution was diluted with dichloromethane (100 ml) and then washed successively with dilute hydrochloric acid solution (2 × 100 ml) and saturated potassium carbonate solution (2 × 100 ml). The organic layer was separated, dried over MgSO4, filtered, and concentrated. The resulting solid was dried in a vacuum oven at 50 °C / 20 mbar. 1.5 g (78%) of (E)-N-(4-cinnamamidobutyl)-2-methylbut-2-enamide (Ia) was obtained as a white solid. The purity according to NMR analysis is approximately 98%. 1H NMR (600 MHz, DMSO-d6) δ = 1.33 - 1.51 (m, 4 H), 1.44 (s, 1 H), 1.45 (s, 1 H), 1.62 - 1.77 (m, 6 H), 1.68 (s, 1 H), 1.72 (s, 1 H), 2.96 - 3.25 (m, 4 H), 3.10 (s, 1 H), 3.17 (s, 1 H), 6.13 - 6.38 (m, 1 H), 6.29 (s, 1 H), 6.50 - 6.71 (m, 1 H), 6.61 (s, 1 H), 7.22 - 7.47 (m, 1 H), 7.34 - 7.43 (m, 2 H), 7.41 (s, 1 H), 7.50 - 7.64 (m, 2 H), 7.55 (s, 1 H), 7.69 - 7.80 (m, 1 H), 7.75 (s, 1 H), 8.01 - 8.36 (m, 1 H), 8.12 (s, 1 H) ppm. 13C NMR (151 MHz, DMSO-d6) δ = 12.41, 13.63, 26.73, 26.79, 38.50, 38.57, 122.34, 127.48, 128.84, 128.96, 129.40, 132.05, 134.97, 138.41, 164.81, 168.31 ppm.

[0032] Example 2: Synthesis of (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamido)butyl)-2-methylbut-2-enamide (Ib) [ka]

[0033] 2a) tert-Butyl (E)-(4-(2-methylbut-2-enamido)butyl)carbamate (3, N-Boc-N'-tiglyl-putrescine): (E)-2-Methylbut-2-enoyl chloride (3.19 g, 26.9 mmol) was added dropwise to a solution of tert-butyl (4-aminobutyl)carbamate (4.6 g, 24.43 mmol) and triethylamine (5 g, 49.4 mmol) in dichloromethane (200 mL) cooled in an ice bath. The resulting solution was stirred at room temperature for 2 h and then washed successively with 1 M HCl (2 × 100 mL), saturated NaHCO (100 mL), and HO (100 mL). The organics were dried over MgSO, filtered, and concentrated. The solid was washed with pentane and then dried in a vacuum oven at 40 °C. There was obtained 6.1 g (92%) of tert-butyl (E)-(4-(2-methylbut-2-enamido)butyl)carbamate (3) as an off-white solid. The purity is >95% by NMR analysis.

[0034] 2b) (E)-N-(4-aminobutyl)-2-methylbut-2-enamide: TFA (8.55 ml, 111 mmol) was added dropwise to a solution of tert-butyl (E)-(4-(2-methylbut-2-enamido)butyl)carbamate (3) (3 g, 11.10 mmol) in dichloromethane (50 ml), giving a colorless solution. After stirring at room temperature for 1 h, the solution was concentrated under reduced pressure (up to 20 mbar) at 50° C. The intermediate (E)-N-(4-aminobutyl)-2-methylbut-2-enamide (4) was obtained as a viscous yellow oil, which was used in the next step 2c without further purification.

[0035] 2c) ((E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamido)butyl)-2-methylbut-2-enamide (Ib): The intermediate (E)-N-(4-aminobutyl)-2-methylbut-2-enamide (4) was dissolved in dichloromethane (150 ml). To the resulting solution was added triethylamine (13.47 g, 133 mmol) with stirring at room temperature. A solution of (E)-3-(4-methoxyphenyl)acryloyl chloride (2.62 g, 13.31 mmol) in dichloromethane (20 ml) was then added dropwise. Stirring was continued for 2 hours, and the solution was then allowed to stand at room temperature overnight. The next day, the solution was diluted with dichloromethane (100 ml) and washed successively with 1 M HCl (3 × 150 ml), saturated NaHCO₃ (2 × 150 ml), and HO (150 ml). The organic layer was dried over MgSO₄, filtered, and concentrated to give 3.3 g of an off-white solid with a purity of approximately 80% by NMR analysis. Purification by silica gel column using DCM / ethyl acetate followed by recrystallization from ethanol gave 1.5 g (41%) of (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamido)butyl)-2-methylbut-2-enamide (Ib) as a white solid. The purity is >98% by NMR analysis. 1H NMR (600 MHz, DMSO-d6) δ = 1.35 - 1.50 (m, 4 H), 1.43 (s, 1 H), 1.44 (s, 1 H), 1.60 - 1.77 (m, 6 H), 1.67 (s, 1 H), 1.72 (s, 1 H), 3.00 - 3.21 (m, 4 H), 3.10 (s, 1 H), 3.15 (s, 1 H), 3.70 - 3.85 (m, 3 H), 3.78 (s, 1 H), 6.17 - 6.36 (m, 1 H), 6.27 (s, 1 H), 6.41 - 6.56 (m, 1 H), 6.96 (d, J=8.95 Hz, 2 H), 7.21 - 7.43 (m, 1 H), 7.43 - 7.56 (m, 2 H), 7.48 (s, 1 H), 7.60 - 7.82 (m, 1 H), 7.74 (s, 1 H), 7.89 - 8.17 (m, 1 H), 8.01 (s, 1 H) ppm. 13C NMR (151 MHz, DMSO-d6) δ = 12.41, 13.63, 26.79, 38.46, 38.59, 55.26, 114.38, 119.85, 127.52, 129.03, 132.05, 138.11, 160.25, 165.12, 168.32 ppm.

[0036] Example 3 Synthesis of (E)-4-methoxy-N-(4-(2-methylbut-2-enamido)butyl)benzamide (1c) [ka]

[0037] 3a) The intermediate (E)-N-(4-aminobutyl)-2-methylbut-2-enamide (4) obtained from Step 2b) of Example 2 was dissolved in dichloromethane (150 ml). To the resulting solution, trimethylamine (4.04 g, 39.9 mmol) was added with stirring at room temperature. A solution of 4-methoxybenzoyl chloride (0.7 g, 4.10 mmol) in dichloromethane (20 ml) was then added dropwise. Stirring was continued for 2 hours, and the solution was then left at room temperature overnight. The next day, the solution was diluted with dichloromethane (100 ml) and washed successively with 1 M HCl (2 × 150 ml), saturated NaHCO (2 × 150 ml), and HO (150 ml). The organic layer was dried over MgSO, filtered, and concentrated to give a slightly yellow solid, which was recrystallized from ethyl acetate, washed with ether, and dried in a vacuum oven at 50 °C. The result was 0.8 g (79%) of (E)-4-methoxy-N-(4-(2-methylbut-2-enamido)butyl)benzamide (Ic) as a white powder. The purity is >95% by NMR analysis. 1H NMR (600 MHz, DMSO-d6) δ = 1.29-1.54 (m, 4 H), 1.61-1.74 (m, 6 H), 3.03- 3.16 (m, 2 H), 3.18-3.28 (m, 2 H), 3.73-3.86 (m, 3 H), 5.82-6.50 (m, 1 H), 6.79-7.08 (m, 2 H), 7.59-7.92 (m, 3 H), 8.21-8.43 (m, 1 H) ppm. 13C NMR (151 MHz, DMSO-d6) δ = 12.55, 13.76, 26.96, 38.50, 38.77, 55.47, 113.55, 127.02, 128.97, 129.07, 132.18, 161.53, 165.68, 168.42 ppm.

[0038] Example 4: Synthesis of a 1:2 mixture of 4-cinnamamidobutyl (E)-2-methylbut-2-enoate (Id) and 4-cinnamamidobutyl 2-methylbut-3-enoate (Ie) [ka]

[0039] 4a) N-(4-hydroxybutyl)cinnamamide (5) A 250 mL round-bottom flask was provided with 4-aminobutan-1-ol (3.21 g, 36.0 mmol) and triethylamine (9.20 mL, 66.0 mmol) in dichloromethane (100 mL). While cooling in an ice / water bath, cinnamoyl chloride (5 g, 30.0 mmol) in 10 mL of dichloromethane was added dropwise. The cooling bath was removed, and stirring was continued at room temperature for 2 hours. The reaction mixture was diluted with dichloromethane and washed with dilute hydrochloric acid solution. The organic layer was separated and washed with saturated sodium bicarbonate solution and brine. The organic layer was dried and evaporated to yield 4.5 g (67%) of N-(4-hydroxybutyl)cinnamamide (5) as an oil. The purity is >95% by NMR analysis. 1H NMR (600 MHz, DMSO-d6) δ = 1.35-1.55 (m, 4 H), 3.09-3.25 (m, 2 H), 3.36- 3.58 (m, 2 H), 4.43 (t, 1 H), 6.61-6.64 (d, 1 H), 7.32-7.43 (m, 4 H), 7.54-7.56 (d, 2 H), 8.11 (br t, 1 H) ppm. 13C NMR (151 MHz, DMSO-d6) δ = 25.89, 30.00, 38.63, 60.45, 122.38, 127.49, 128.97, 129.40, 134.99, 138.40, 164.81 ppm.

[0040] 4b) 4-Cinnamamidobutyl (E)-2-methylbut-2-enoate (Id) and 4-Cinnamamidobutyl 2-methylbut-3-enoate (Ie) N-(4-Hydroxybutyl)cinnamamide (5) (1 g, 4.56 mmol) was dissolved in dichloromethane (25 mL). Triethylamine (1.271 mL, 9.12 mmol) was added with stirring. Then, (E)-2-methylbut-2-enoyl chloride (0.595 g, 5.02 mmol) was added dropwise with stirring. The exothermic reaction began to reflux. Stirring was continued at room temperature for 3 hours. The reaction mixture was diluted with ether and washed with dilute hydrochloric acid solution. The organic layer was separated, washed with saturated sodium bicarbonate solution, dried, and concentrated. The residue was purified by flash column chromatography. Eluent: dichloromethane / methanol, 0-3% methanol. 0.7 g of products Id and Ie (51%) were obtained in a ratio of 1:2. 1H NMR (600 MHz, DMSO-d6) δ = 1.16 - 1.20 (m, 3 H), 1.45 - 1.56 (m, 3 H), 1.57 - 1.67 (m, 3 H), 1.74 - 1.78 (m, 3 H), 3.16 - 3.23 (m, 4 H), 4.03 -4.07 (m, 2 H), 4.07 - 4.11 (m, 1 H,) 5.06 - 5.17 (m, 2 H), 5.84 - 5.92 (m, 1 H), 6.59 - 6.64 (m, 1 H), 6.74 - 6.81 (m, 1 H), 7.35 - 7.39 (m, 2 H), 7.39 - 7.41 (m, 2 H), 7.41 - 7.44 (m, 3 H), 7.53 - 7.59 (m, 3 H), 8.04 - 8.21 (m, 1 H) ppm. 13C NMR (151 MHz, DMSO-d6) δ = 12.50, 14.70, 16.90, 26.18, 26.24, 26.32, 38.73, 38.78, 40.56, 43.28, 64.23, 64.37, 116.48, 122.78, 128.01, 129.47, 129.92, 135.46, 137.67, 137.86, 139.00, 165.36, 174.09 ppm.

[0041] Example 5: Synthesis of 4-((E)-2-methylbut-2-enamido)butylcinnamate (If) [ka]

[0042] 5a) (E)-N-(4-hydroxybutyl)-2-methylbut-2-enamide (6) 4-Aminobutan-1-ol (3.01 g, 33.7 mmol) was dissolved in dichloromethane (50 ml). Triethylamine (4.70 ml, 33.7 mmol) was added with stirring. The solution was cooled in an ice / water bath, and (E)-2-methylbut-2-enoyl chloride (2 g, 16.87 mmol) was added dropwise. The cooling bath was removed, and stirring was continued at room temperature for 3 hours. The reaction mixture was diluted with dichloromethane and washed with dilute hydrochloric acid solution. The organic layer was separated, washed with potassium carbonate solution, dried, and concentrated. The residue was purified by flash column chromatography. Eluent: DCM / methanol, 0-3% methanol. 1 g of oil was obtained. The purity is >95% by NMR analysis. 1H NMR (600 MHz, DMSO-d6) δ = 1.28 - 1.51 (m, 4 H), 1.62 - 1.70 (d, 3 H), 1.74 (s, 3 H), 3.00 - 3.13 (m, 2 H), 3.36 - 3.40 (m, 2 H), 4.30 - 4.36 (t, 1 H), 6.25 - 6.30 (q, 1 H), 7.59 - 7.86 (br t, 1 H) ppm. 13C NMR (151 MHz, DMSO-d6) δ = 12.41, 13.62, 25.90, 30.02, 38.79, 60.54, 128.74, 132.11, 168.28 ppm.

[0043] 5b) 4-((E)-2-methylbut-2-enamido)butylcinnamate (If) To (E)-N-(4-hydroxybutyl)-2-methylbut-2-enamide (6, 1 g, 5.84 mmol) was added cinnamoyl chloride (0.973 g, 5.84 mmol). The reaction mixture was stirred at 60° C. for 3 h. It was then briefly heated at 100° C. The crude product was purified by flash column chromatography, eluent DCM / methanol with 1% methanol, to give 1.5 g of a colorless oil. 1H NMR (600 MHz, DMSO-d6) δ = 1.39 - 1.77 (m, 10 H), 3.05 - 3.22 (q, 2 H), 4.08 -4.21 (t, 2 H), 6.18 - 6.38 (q, 1 H), 6.59 - 6.71 (d, 1 H), 7.29 - 7.50 (m, 3 H), 7.62 - 7.82 (m, 4 H) ppm. 13C NMR (151 MHz, DMSO-d6) δ = 12.54, 13.75, 25.88, 30.86, 38.53, 63.98, 118.24, 128.34, 128.54, 129.08, 130.63, 132.17, 134.18, 144.62, 165.43, 168.48 ppm.

[0044] Example 6: Taste evaluation - comparison with MSG An aqueous NaCl solution (0.5% by weight) was prepared. To this base the following was added: a) 30 ppm of compound Ia (sample 6a); b) 200 ppm MSG (sample 6b, benchmark). The taste of the two samples, 6a and 6b, was evaluated by five trained panelists who were asked to rate the intensity of sample 6a as a difference from sample 6b and to describe the overall effect. Typically, the following descriptors are used to describe the effect: umami, salty, bitter, and overall sweet. The taste of sample 6a was described as umami, brothy, and long-lasting. The umami at bitterness level was marked as slightly higher than the benchmark. Overall, sample 6a was preferred over sample 6b.

[0045] Example 7: Taste evaluation - comparison with further derivatives An aqueous NaCl solution (0.5% by weight) was prepared. To this base the following was added: a) 20 ppm of compound Ia (sample 7a); b) 20 ppm of compound Ib (sample 7b); c) 20 ppm of compound Ic (sample 7c). The taste of the three samples 7a, 7b, and 7c was evaluated by five trained panelists. The taste of Sample 7b was described as more umami, stronger, longer lasting, sweeter but with off-notes, animalic, floral sweet compared to Sample 7a. The taste of sample 7c was described as having more umami and a cleaner umami flavor than sample 7a.

[0046] Example 8: Taste evaluation of amide ester analogs An aqueous solution of NaCl (0.5 wt %) and MSG (0.05 wt %) was prepared. To this base was added: a) 20 ppm mixture of compounds (Id+Ie) in a ratio of 1:2 (sample 8a). b) Compound If (sample 8b) 20 ppm. A group of four experienced tasters compared samples 8a and 8b with the pure base. The group unanimously recognized sample 8a as having more umami than the base, plus some perceived bitterness. Unanimously, the group perceived sample 8b to have more umami than the base. The taste was described as a pleasant taste experience.

Claims

1. Formula (I) 【Chemistry 1】 【Chemistry 2】 and X, Y=—NH— or —O—, where at least X or Y is —NH—, the use of one or more compounds according to the formula 【Transformation 3】 represents a carbon-carbon single or double bond, with one carbon-carbon double bond being present at either C2 or C3; A wavy bond indicates an arbitrary arrangement of adjacent double bonds; Said use as an ingredient to impart, enhance, improve or modify the umami taste sensation of a consumable composition.

2. One or more compounds according to formula (I) are represented by formula (II) 【Chemistry 4】 【Transformation 5】 10. The use of claim 1 as an ingredient to impart, enhance, improve or modify the umami taste sensation of a consumable composition further defined by:

3. 2. The use of claim 1, wherein the one or more compounds are selected from the group consisting of (E)-N-(4-cinnamamidobutyl)-2-methylbut-2-enamide, (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamido)butyl)-2-methylbut-2-enamide, (E)-4-methoxy-N-(4-(2-methylbut-2-enamido)butyl)benzamide, 4-cinnamamidobutyl (E)-2-methylbut-2-enoate, 4-cinnamamidobutyl 2-methylbut-3-enoate, and 4-((E)-2-methylbut-2-enamido)butylcinnamate.

4. A compound according to formula (I) according to one or more claims 1, An umami flavor composition for imparting, enhancing, improving or modifying the umami taste sensation of a consumable composition.

5. 5. The umami flavor composition of claim 4, wherein the one or more compounds according to formula (I) are selected from the group consisting of (E)-N-(4-cinnamamidobutyl)-2-methylbut-2-enamide, (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamido)butyl)-2-methylbut-2-enamide, (E)-4-methoxy-N-(4-(2-methylbut-2-enamido)butyl)benzamide, 4-cinnamamidobutyl (E)-2-methylbut-2-enoate, 4-cinnamamidobutyl 2-methylbut-3-enoate, and 4-((E)-2-methylbut-2-enamido)butylcinnamate.

6. (i) at least one compound according to formula (I) as defined in claim 1 or an umami flavor composition as defined in claim 4 or 5; and (ii) Product-based 1. A consumable composition comprising:

7. Formula (I) 【Transformation 6】 【Transformation 7】 and X, Y=—NH— or —O—, wherein at least X or Y is —NH—, a compound in the form of any one of its stereoisomers or a mixture thereof, according to the formula 【Transformation 8】 represents a carbon-carbon single or double bond, provided that one of the dotted lines represents a double bond and the other represents a single bond; A wavy bond indicates an arbitrary arrangement of adjacent double bonds; 10. A method of providing a consumable composition having an umami taste sensation, comprising adding to the consumable composition.

8. Formula (I) 【Chemistry 9】 【Chemistry 10】 and X, Y=—NH— or —O—, wherein at least X or Y is —NH—, a compound in the form of any one of its stereoisomers or a mixture thereof, wherein: 【Chemistry 11】 represents a carbon-carbon single or double bond, with one carbon-carbon double bond being present at either C2 or C3; The wavy bonds indicate an unspecified arrangement of adjacent double bonds, provided that the compound is not (E)-N-(4-cinnamamidobutyl)-2-methylbut-2-enamide.

9. 9. The compound of claim 8, wherein the compound is selected from the group consisting of (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamido)butyl)-2-methylbut-2-enamide, (E)-4-methoxy-N-(4-(2-methylbut-2-enamido)butyl)benzamide, 4-cinnamamidobutyl (E)-2-methylbut-2-enoate, 4-cinnamamidobutyl 2-methylbut-3-enoate, and 4-((E)-2-methylbut-2-enamido)butylcinnamate.

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