Improvements in or relating to organic compounds

Abstract

Use of a compound of formula (I) as a umami flavor enhancer, wherein X, Y = -NH- or -O-, with at least X or Y being -NH-, the compound being in the form of any one of its stereoisomers or a mixture thereof, wherein represents a carbon-carbon single bond or double bond, and wherein one carbon-carbon double bond is present at C2 or C3, and the wavy bond represents the unspecified configuration of adjacent double bonds.

Description

[0001] The present invention relates to umami flavorings and methods for their production. The present invention relates to compounds providing umami and savoury flavor, and their use in compositions and consumer products.

[0002] Umami is a flavor sensation commonly associated with Asian cuisine. It has been described as delicious or meaty and is characteristic of broths and cooked meats. Additionally, improved umami helps make low-salt products more palatable. Traditionally, umami has been achieved by adding monosodium glutamate (MSG) to foods. However, it is believed that some consumers are adversely affected by glutamates, particularly MSG, and there is still a need for glutamate-free compounds to replace or reduce reliance on these compounds to modify the umami and savoury flavor of consumer products.

[0003] Amides of cinnamic acid derivatives and aromatic amines from natural sources have been reported as natural or nature-identical umami potentiators in US2012308703A1, WO2013000673A1 or WO2014083202A1. Flavor compositions containing such amides and other substances are disclosed in WO2019063069A1. A specific class of cinnamamides that may produce a trigeminal effect is the subject of the recently published WO2019063069A1.

[0004] It has now surprisingly been found that certain putrescine bisamides and amide ester analogues, namely those of putrescine (butane-1,4-diamine) and 4-aminobutan-1-ol, which on the one hand have a moiety such as cinnamic acid, a cinnamic acid derivative or 4-methoxybenzoic acid and on the other hand have a moiety of tiglic acid ((2E)-2-methylbut-2-enoic acid), can be used as umami potentiators.

[0005] Accordingly, in a first aspect of the present invention, there is provided the use of certain putrescine bisamides and amide ester analogues as ingredients to impart, enhance, improve or modify the umami of a consumer product composition.

[0006] There is also provided a flavor composition comprising a flavor ingredient and certain putrescine bisamides or amide ester analogues.

[0007] There is also provided a consumer product composition having umami, said umami being provided at least in part by certain putrescine bisamides or amide ester analogues present therein.

[0008] In another aspect of the present invention, there are provided novel putrescine bisamides and amide ester analogues.

[0009] In a first aspect of the present invention, there is provided the use of one or more compounds of formula (I) as ingredients to impart, enhance, improve or modify the umami of a consumer product composition

[0010]

[0011] wherein

[0012] and wherein X, Y = -NH- or -O-, with at least X or Y being -NH-

[0013] the compound is in the form of any one of its stereoisomers or a mixture thereof, wherein

[0014] represents a single or double carbon-carbon bond, and one of the carbon-carbon double bonds is present at C2 or C3,

[0015] the wavy bond represents the unspecified configuration of adjacent double bonds.

[0016] In one embodiment of the present invention, there is provided the use of one or more compounds of formula (II) as an ingredient for imparting, enhancing, improving or modifying the umami taste of a consumer product composition

[0017]

[0018] wherein

[0019] the compound is in the form of any one of its stereoisomers or a mixture thereof, wherein

[0020] the wavy bond represents the unspecified configuration of adjacent double bonds.

[0021] The compound of formula (II) is a bisamide and corresponds to the compound of formula (I), wherein X and Y are -NH-, and one of the carbon-carbon double bonds is present at C2.

[0022] In another embodiment of the present invention, there is provided the use of a compound of formula (I) as defined above, wherein the compound is selected from (E)-N-(4-cinnamoylaminobutyl)-2-methylbut-2-enamide, (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamino)butyl)-2-methylbut-2-enamide, (E)-4-methoxy-N-(4-(2-methylbut-2-enoylamino)butyl)benzamide, (E)-4-cinnamoylaminobutyl 2-methylbut-2-enoate, 4-cinnamoylaminobutyl 2-methylbut-3-enoate, and 4-((E)-2-methylbut-2-enoylamino)butyl cinnamate.

[0023] In another embodiment of the present invention, there is provided the use of a mixture of compounds of formula (I) as defined above. More specifically, there is provided the use of a mixture of (E)-4-cinnamoylaminobutyl 2-methylbut-2-enoate and 4-cinnamoylaminobutyl 2-methylbut-3-enoate in a ratio of 1:2.

[0024] In another embodiment of the present invention, there is provided the use of a compound of formula (II) as defined above, wherein the compound is selected from (E)-N-(4-cinnamoylaminobutyl)-2-methylbut-2-enamide, (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamino)butyl)-2-methylbut-2-enamide, and (E)-4-methoxy-N-(4-(2-methylbut-2-enoylamino)butyl)benzamide.

[0025] There is also provided a umami flavor composition comprising one or more compounds of formula (I) or formula (II) and one or more other flavor ingredients.

[0026] The compound of formula (I) or formula (II) can be used alone as the sole flavor ingredient in a consumer product composition or in combination with additional flavor ingredients to provide a flavor composition ready to be added to a consumer product composition. The other flavor ingredients can include other umami flavor enhancers and / or umami or taste enhancers, including MSG. The use of the compound of formula (I) or formula (II) allows for a significant reduction in the level of MSG and, in some cases, a complete elimination of MSG.

[0027] The other umami flavor enhancers and / or the umami or taste enhancers include, but are not limited to: L-Glu (glutamic acid, glutamate, for example in the form of its salts such as monosodium glutamate, monopotassium glutamate, monoammonium glutamate, calcium diglutamate, magnesium diglutamate), L-Asp (L-asparagine or its salts), 5'-ribonucleotides or their salts, including but not limited to calcium 5'-ribonucleotide, disodium 5'-ribonucleotide, and dipotassium 5'-ribonucleotide (for example, inosinic acid, guanylic acid, adenylic acid, inosinates, guanylates, and adenylates, including 5'-guanylic acid, 5'-inosinic acid, and 5'-adenylic acid and their salts such as disodium guanylate, disodium inosinate, disodium adenylate; dipotassium guanylate, dipotassium inosinate, dipotassium adenylate, calcium guanylate, calcium inosinate, calcium adenylate), maltol, ethyl maltol, glycine, L-leucine, autolyzed or hydrolyzed proteins (such as autolyzed yeast, hydrolyzed yeast, hydrolyzed vegetable protein), Koji-Aji (a nucleotide-rich yeast extract containing fermented wheat gluten and maltodextrin, also containing glutamate produced by Ajinomoto Food Ingredients), and natural preparations or extracts containing one or more of the above, for example extracts, broths, or concentrates from vegetables (including mushrooms, shiitake mushrooms, soybeans, tomatoes, potatoes, whey, kelp / seaweed), grains, meat, fish (such as shellfish, fish roe (masago)), milk, cheese, and egg yolks, in fresh or fermented, partially or completely hydrolyzed forms (such as various hydrolyzed proteins).

[0028] Specific examples of said other umami flavor enhancers and / or said umami or deliciousness enhancers include the compounds described in UK Patent Application No. 0913804 and International Application No. PCT / EP2010 / 059916. Other non-limiting examples of compounds that impart umami flavor and enhance umami flavor include those described in EP1642886, WO2005 / 015158, EP1312268, WO2003 / 088768, EP1291342, and WO2006 / 003107, all of which references are incorporated herein by reference.

[0029] In addition to other umami flavor enhancers and / or umami or deliciousness enhancers, other flavor ingredients that can be used in combination with the compounds of formula (I) or formula (II) to provide a flavor composition can be selected from natural flavorings, artificial flavorings, spices, seasonings, etc., synthetic flavor oils and flavor aromatics and / or oils, oleoresins, essential oils, distillates, and extracts derived from plants, leaves, flowers, fruits, etc. Generally, any flavoring or food additive can be used, such as those described in Chemicals Used in Food Processing by the National Academy of Sciences, Publication 1274, pages 63 - 258. This publication is incorporated herein by reference.

[0030] The compound of formula (I) or formula (II) can be used directly in a consumer product composition, or it can form part of a flavor composition, particularly an umami flavor composition, which is subsequently mixed with the consumer product composition. In a specific embodiment, based on the flavor composition, the compound of formula (I) or formula (II) can be used in an amount of about 0.001 to 100% or 0.01 to 10%, more preferably 0.1 to 10%, even more preferably 0.5 to 5% by weight.

[0031] The compound of formula (I) or formula (II) can additionally be combined with one or more ingredients or excipients commonly used in flavor compositions (such as carrier materials and other auxiliaries commonly used in the art) for use in flavor compositions. Suitable excipients for flavor compositions are well-known in the art and include, for example, but are not limited to solvents (including water, alcohols, ethanol, oils, fats, vegetable oils, and miglyol), binders, diluents, disintegrants, lubricants, flavorings, colorants, preservatives, antioxidants, emulsifiers, stabilizers, flavor enhancers, anti-caking agents, etc.

[0032] Examples of such carriers or diluents for perfume compositions can be found, for example, in "Perfume and Flavour Materials of Natural Origin", S. Arctander, Ed., Elizabeth, N.J., 1960; "Perfume and Flavour Chemicals", S. Arctander, Ed., Volumes I & II, Allured Publishing Corporation, Carol Stream, USA, 1994; “Flavourings”, E. Ziegler and H. Ziegler (ed.), Wiley-VCH Weinheim, 1998, and “CTFA Cosmetic Ingredient Handbook”, J.M. Nikitakis (ed.), 1st Edition, The Cosmetic, Toiletry and Fragrance Association, Inc., Washington, 1988.

[0033] Other suitable and desirable ingredients of perfume compositions are described in standard textbooks, such as "Handbook of Industrial Chemical Additives", ed. M. and I. Ash, 2nd Edition, (Synapse 2000).

[0034] There is further provided a consumer product composition having a umami perfume, the umami perfume being provided at least in part by a compound of formula (I) or formula (II) present therein.

[0035] There is also provided a consumer product composition comprising at least one compound of formula (I) or formula (II), or a umami perfume composition comprising one or more compounds of formula (I) or formula (II); and a product base.

[0036] The proportion of the compound of formula (I) or formula (II) used in the consumer product 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 that required for complete MSG replacement. This proportion can vary within wide limits, typically between 0.01 ppm and 10,000 ppm, more particularly between 0.1 ppm and 1,000 ppm, still more particularly between 1 ppm and 500 ppm or 5 - 50 ppm, by weight of the consumer product composition. However, these are only general indications of useful proportions, and a skilled perfumer can use proportions outside these ranges for specific effects.

[0037] "Consumer product composition" means any composition that is taken into the mouth for ultimate spitting out or ingestion. The composition can be in any physical form, solid, liquid or gas. Non-limiting examples include all foods, food additives, nutraceuticals, drugs and any products placed in the mouth, including (but not limited to) chewing gums, oral care products and oral hygiene products, including but not limited to cereal products, rice products, cassava products, sago products, baked products, cookie products, pastry products, bread products, confectionery products, dessert products, gums, chewing gums, flavorings or food / drink containers coated with flavorings, yeast products, baking powders, salt and spice products, snack foods, savory products, mustard products, vinegar products, sauces (condiments), soups, seasonings, ready-to-eat meals, gravies, nuts and nut products, processed foods, vegetable products, meat and meat products, egg products, milk and dairy products, yogurts, cheese products, butter and butter substitute products, milk substitute products, soy products, edible oils and fat products, beverages, carbonated beverages, alcoholic beverages such as beer, wine and spirits, non-alcoholic beverages such as soft drinks or other flavored products, including forms that require 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, flavorings, gelatin, pharmaceutical and non-pharmaceutical gums, tablets, lozenges, drops, emulsions, elixirs. Syrups and other products for making beverages, and combinations thereof.

[0038] In particular, the compounds of formula (I) or formula (II) are suitable for consumer product compositions selected from savory products, including snacks, soups, broths, sauces, meat / protein and ready-to-eat meals, etc.

[0039] "Product base" means the combination of all the usual and generally recognized ingredients in the art required for a particular consumer product composition.

[0040] In another aspect of the present invention, there is provided a method of providing a consumer product composition having umami flavor, the method comprising the step of adding one or more compounds of formula (I) or formula (II) to the consumer product composition.

[0041] In another aspect of the present invention, there is provided a compound of formula (I)

[0042]

[0043] wherein

[0044] and wherein X, Y = -NH- or -O-, with at least X or Y being -NH-,

[0045] The compound is in the form of any one of its stereoisomers or a mixture thereof, wherein

[0046] represents a single or double carbon-carbon bond, and one of the carbon-carbon double bonds is present at C2 or C3,

[0047] the wavy bond represents the unspecified configuration of adjacent double bonds,

[0048] provided that the compound is not (E)-N-(4-cinnamoylaminobutyl)-2-methylbut-2-enamide.

[0049] In the extract of Aglaia gracilis, a new class of putrescine bisamides has been found (Inada et al., Phytochemistry 53, 2000, 1091 - 1095). Two of them have been identified as cinnamamides, including (E)-N-(4-cinnamoylaminobutyl)-2-methylbut-2-enamide. Their syntheses have been reported (Deterbeck et al., Tetrahedron, 58(2002)6887 - 6893).

[0050] In particular, the compounds of formula (I) are selected from (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamino)butyl)-2-methylbut-2-enamide, (E)-4-methoxy-N-(4-(2-methylbut-2-enamido)butyl)benzamide, (E)-4-cinnamoylaminobutyl 2-methylbut-2-enoate, 4-cinnamoylaminobutyl 2-methylbut-3-enoate, and 4-((E)-2-methylbut-2-enamido)butyl cinnamate.

[0051] The compounds of formula (I) or formula (II) can be obtained using direct synthesis methods known to those skilled in the art and readily available starting materials. Specific reaction conditions are further described in the examples.

[0052] The present invention is now further described by non-limiting examples that describe specific embodiments below. Examples:

[0053] Example 1: Synthesis of (E)-N-(4-cinnamoylaminobutyl)-2-methylbut-2-enamide (Ia):

[0054]

[0055] 1a) tert-Butyl (4-cinnamoylaminobutyl)carbamate (1):

[0056] 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 with an ice bath. After stirring at room temperature for 2 h, the reaction mixture was washed successively with 1 M HCl (2 x 100 ml), saturated NaHCO 3 (100 ml) and H 2 O (100 ml). The organic phase was dried over MgSO 4 , filtered and concentrated. The resulting solid was washed with MTBE / pentane and then dried in a vacuum oven at 40 °C. 7.5 g (93%) of tert-butyl (4-cinnamoylaminobutyl)carbamate (1) were obtained as a white powder.

[0057] Analysis by NMR showed a purity > 95%.

[0058] 1H NMR (600 MHz, DMSO-d6) δ = 1.15 - 1.58 (m, 13H), 2.82 - 3.00 (m, 2H), 3.08 - 3.23 (m, 2H), 6.55 - 6.70 (m, 1H), 6.77 - 6.92 (m, 1H), 7.29 - 7.47 (m, 4H), 7.49 - 7.66 (m, 2H), 8.03 - 8.32 (m, 1H) ppm.

[0059] 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.

[0060] 1b) N-(4-aminobutyl)cinnamide (2):

[0061] TFA (4.84 ml, 62.8 mmol) was added to a solution of tert-butyl (4-cinnamoylaminobutyl)carbamate (1) (2 g, 6.28 mmol) in dichloromethane (100 mL). After stirring at room temperature for 2 h, the volatiles were removed under reduced pressure (down to 20 mbar) at 50 °C. The intermediate N-(4-aminobutyl)cinnamide (2, N-(4-aminobutyl)-3-phenyl-prop-2-enamide), obtained as a viscous yellow oil, was used in the next step 1c) without any further purification.

[0062] 1c) (E)-N-(4-cinnamoylaminobutyl)-2-methylbut-2-enamide (Ia):

[0063] Dissolve the intermediate N-(4-aminobutyl)cinnamamide (2) in dichloromethane. Add triethylamine (5.25 ml, 37.7 mmol) to the resulting solution while stirring at room temperature. Then, dropwise add a solution of (E)-2-methylbut-2-enoyl chloride (1.043 g, 8.79 mmol) in dichloromethane (10 mL). Stir continuously for 2 hours, and then let the solution stand overnight at room temperature. The next day, dilute the solution with dichloromethane (100 ml), and then wash it successively with dilute hydrochloric acid solution (2 × 100 ml) and saturated potassium carbonate solution (2 × 100 ml). Separate the organic layer and dry it with MgSO 4 Dry, filter, and concentrate. Dry the obtained solid in a vacuum oven at 50 °C / 20 mbar.

[0064] 1.5 g (78%) of (E)-N-(4-cinnamoylaminobutyl)-2-methylbut-2-enamide (Ia), a white solid.

[0065] The purity is about 98% (by NMR analysis).

[0066] 1H NMR (600 MHz, DMSO-d6) δ = 1.33 - 1.51 (m, 4H), 1.44 (s, 1H), 1.45 (s, 1H), 1.62 - 1.77 (m, 6H), 1.68 (s, 1H), 1.72 (s, 1H), 2.96 - 3.25 (m, 4H), 3.10 (s, 1H), 3.17 (s, 1H), 6.13 - 6.38 (m, 1H), 6.29 (s, 1H), 6.50 - 6.71 (m, 1H), 6.61 (s, 1H), 7.22 - 7.47 (m, 1H), 7.34 - 7.43 (m, 2H), 7.41 (s, 1H), 7.50 - 7.64 (m, 2H), 7.55 (s, 1H), 7.69 - 7.80 (m, 1H), 7.75 (s, 1H), 8.01 - 8.36 (m, 1H), 8.12 (s, 1H) ppm.

[0067] 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.

[0068] Example 2: Synthesis of (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamino)butyl)-2-methylbut-2-enamide (1b)

[0069]

[0070] 2a) (E)-(4-(2-Methylbut-2-enamido)butyl)carbamic acid tert-butyl ester (3,N-Boc-N’-methylcrotonyl-putrescine):

[0071] Drop (E)-2-methylbut-2-enoyl chloride (3.19 g, 26.9 mmol) into a solution of (4-aminobutyl)carbamic acid tert-butyl ester (4.6 g, 24.43 mmol) and triethylamine (5 g, 49.4 mmol) in dichloromethane (200 mL) cooled with an ice bath. Stir the resulting solution at room temperature for 2 hours, then wash it successively with 1M HCl (2 x 100 ml), saturated NaHCO 3 (100 ml) and H 2 O (100 ml). Dry the organic phase with MgSO 4 , filter and concentrate. Wash the solid with pentane and then dry it in a vacuum oven at 40 °C.

[0072] Obtain 6.1 g (92%) of (E)-(4-(2-methylbut-2-enamido)butyl)carbamic acid tert-butyl ester (3) as an off-white solid.

[0073] The purity is >95% by NMR analysis.

[0074] 2b) (E)-N-(4-Aminobutyl)-2-methylbut-2-enamide (4, N-mono-methylcrotonyl-putrescine):

[0075] Drop TFA (8.55 ml, 111 mmol) into a solution of (E)-(4-(2-methylbut-2-enamido)butyl)carbamic acid tert-butyl ester (3) (3 g, 11.10 mmol) in dichloromethane (50 mL) to obtain a colorless solution. After stirring at room temperature for 1 hour, concentrate the solution under reduced pressure (down to 20 mbar) at 50 °C. Obtain the intermediate (E)-N-(4-aminobutyl)-2-methylbut-2-enamide (4) as a viscous yellow oil, which is used in the next step 2c without any further purification.

[0076] 2c) (E)-N-(4-((E)-3-(4-Methoxyphenyl)acrylamido)butyl)-2-methylbut-2-enamide (1b):

[0077] Dissolve the intermediate (E)-N-(4-aminobutyl)-2-methylbut-2-enamide (4) in dichloromethane (150 mL). Add triethylamine (13.47 g, 133 mmol) to the resulting solution while stirring at room temperature. Then, dropwise add a solution of ((E)-3-(4-methoxyphenyl)acryloyl chloride (2.62 g, 13.31 mmol) in dichloromethane (20 mL), continue stirring for 2 hours, and then let the solution stand overnight at room temperature. The next day, dilute the solution with dichloromethane (100 mL) and wash it successively with 1 M HCl (3 x 150 mL), saturated NaHCO 3 (2 x 150 mL) and H 2 O (150 mL). Dry the organic layer over MgSO 4 , filter, and concentrate. 3.3 g of a yellowish-white solid is obtained, which has a purity of approximately 80% by NMR analysis.

[0078] Purify using DCM / ethyl acetate by silica gel column chromatography and then recrystallize from ethanol to obtain 1.5 g (41%) of (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamido)butyl)-2-methylbut-2-enamide (1b) as a white solid.

[0079] By NMR analysis, the purity > 98%.

[0080] 1H NMR (600 MHz, DMSO-d6) δ = 1.35 - 1.50 (m, 4H), 1.43 (s, 1H), 1.44 (s, 1H), 1.60 - 1.77 (m, 6H), 1.67 (s, 1H), 1.72 (s, 1H), 3.00 - 3.21 (m, 4H), 3.10 (s, 1H), 3.15 (s, 1H), 3.70 - 3.85 (m, 3H), 3.78 (s, 1H), 6.17 - 6.36 (m, 1H), 6.27 (s, 1H), 6.41 - 6.56 (m, 1H), 6.96 (d, J = 8.95 Hz, 2H), 7.21 - 7.43 (m, 1H), 7.43 - 7.56 (m, 2H), 7.48 (s, 1H), 7.60 - 7.82 (m, 1H), 7.74 (s, 1H), 7.89 - 8.17 (m, 1H), 8.01 (s, 1H) ppm.

[0081] 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.

[0082] Example 3: Synthesis of (E)-4-methoxy-N-(4-(2-methylbut-2-enamido)butyl)benzamide (1c)

[0083]

[0084] 3a) Dissolve the intermediate (E)-N-(4-aminobutyl)-2-methylbut-2-enamide (4) obtained from step 2b) of Example 2 in dichloromethane (150 ml). While stirring at room temperature, add trimethylamine (4.04 g, 39.9 mmol) to the resulting solution, and then dropwise add a solution of 4-methoxybenzoyl chloride (0.7 g, 4.10 mmol) in dichloromethane (20 ml). Stir continuously for 2 hours, and then let the solution stand overnight at room temperature. The next day, dilute the solution with dichloromethane (100 ml) and wash it successively with 1M HCl (2 x 150 ml), saturated NaHCO 3 aqueous solution (2 x 150 ml) and H 2 O (150 ml). Dry the organic layer with MgSO 4 , filter and concentrate to obtain a light yellow solid. Recrystallize it from ethyl acetate, wash with diethyl ether, and dry in a vacuum oven at 50 °C. 0.8 g (79%) of (E)-4-methoxy-N-(4-(2-methylbut-2-enamido)butyl)benzamide (1c) is obtained as a white powder.

[0085] The purity is >95% by NMR analysis.

[0086] 1H NMR (600 MHz, DMSO-d6) δ = 1.29 - 1.54 (m, 4H), 1.61 - 1.74 (m, 6H), 3.03 - 3.16 (m, 2H), 3.18 - 3.28 (m, 2H), 3.73 - 3.86 (m, 3H), 5.82 - 6.50 (m, 1H), 6.79 - 7.08 (m, 2H), 7.59 - 7.92 (m, 3H), 8.21 - 8.43 (m, 1H) ppm.

[0087] 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.

[0088] Example 4: Synthesis of a mixture of (E)-4-cinnamoylaminobutyl 2-methylbut-2-enoate (Id) and 4-cinnamoylaminobutyl 2-methylbut-3-enoate (Ie) (1:2)

[0089]

[0090] 4a) N-(4-Hydroxybutyl)cinnamide (5)

[0091] In a 250 mL round-bottom flask, 4-aminobutan-1-ol (3.21 g, 36.0 mmol) and triethylamine (9.20 mL, 66.0 mmol) in dichloromethane (100 mL) were provided. Cinnamoyl chloride (5 g, 30.0 mmol) in 10 mL of dichloromethane was added dropwise while cooling with an ice / water bath. The cooling bath was removed and stirring was continued at room temperature for 2 h. 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 give 4.5 g (67%) of N-(4-hydroxybutyl)cinnamide (5) as an oil.

[0092] The purity was >95% by NMR analysis.

[0093] 1H NMR (600 MHz, DMSO-d6) δ = 1.35 - 1.55 (m, 4H), 3.09 - 3.25 (m, 2H), 3.36 - 3.58 (m, 2H), 4.43 (t, 1H), 6.61 - 6.64 (d, 1H), 7.32 - 7.43 (m, 4H), 7.54 - 7.56 (d, 2H), 8.11 (br t, 1H) ppm.

[0094] 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.

[0095] 4b) (E)-4-cinnamoylaminobutyl 2-methylbut-2-enoate (Id) and 4-cinnamoylaminobutyl 2-methylbut-3-enoate (Ie)

[0096] Dissolve N-(4-hydroxybutyl)cinnamamide (5) (1 g, 4.56 mmol) in dichloromethane (25 mL). Add triethylamine (1.271 mL, 9.12 mmol) with stirring. Then, dropwise add (E)-2-methylbut-2-enoyl chloride (0.595 g, 5.02 mmol) with stirring. An exothermic reaction starts to reflux. Stir continuously at room temperature for 3 hours. Dilute the reaction mixture with diethyl ether and wash it with dilute hydrochloric acid solution. Separate the organic layer, wash it with saturated sodium bicarbonate solution, dry and concentrate. Purify the residue by flash column chromatography. Eluent: dichloromethane / methanol, 0 - 3% methanol.

[0097] 0.7 g of products Id and Ie (51%) were obtained, with a ratio of 1:2.

[0098] 1H NMR (600 MHz, DMSO-d6) δ = 1.16 - 1.20 (m, 3H), 1.45 - 1.56 (m, 3H), 1.57 - 1.67 (m, 3H), 1.74 - 1.78 (m, 3H), 3.16 - 3.23 (m, 4H), 4.03 - 4.07 (m, 2H), 4.07 - 4.11 (m, 1H,), 5.06 - 5.17 (m, 2H), 5.84 - 5.92 (m, 1H), 6.59 - 6.64 (m, 1H), 6.74 - 6.81 (m, 1H), 7.35 - 7.39 (m, 2H), 7.39 - 7.41 (m, 2H), 7.41 - 7.44 (m, 3H), 7.53 - 7.59 (m, 3H), 8.04 - 8.21 (m, 1H) ppm.

[0099] 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.

[0100] Example 5: Synthesis of 4-((E)-2-methylbut-2-enamido)butyl cinnamate (If)

[0101]

[0102] 5a) (E)-N-(4-hydroxybutyl)-2-methylbut-2-enamide (6)

[0103] 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 with 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 h. 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 an oil was obtained.

[0104] Analysis by NMR showed a purity > 95%.

[0105] 1H NMR (600 MHz, DMSO-d6) δ = 1.28 - 1.51 (m, 4H), 1.62 - 1.70 (d, 3H), 1.74 (s, 3H), 3.00 - 3.13 (m, 2H), 3.36 - 3.40 (m, 2H), 4.30 - 4.36 (t, 1H), 6.25 - 6.30 (q, 1H), 7.59 - 7.86 (brt, 1H) ppm.

[0106] 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.

[0107] 5b) 4-((E)-2-Methylbut-2-enamido)butyl cinnamate (If)

[0108] Cinnamoyl chloride (0.973 g, 5.84 mmol) was added to (E)-N-(4-hydroxybutyl)-2-methylbut-2-enamide (6.1 g, 5.84 mmol). The reaction mixture was stirred at 60 °C for 3 h. Then it was heated briefly at 100 °C. The crude product was purified by flash column chromatography, eluent DCM / methanol containing 1% methanol, to give 1.5 g of a colorless oil.

[0109] 1H NMR (600 MHz, DMSO-d6) δ = 1.39 - 1.77 (m, 10H), 3.05 - 3.22 (q, 2H), 4.08 - 4.21 (t, 2H), 6.18 - 6.38 (q, 1H), 6.59 - 6.71 (d, 1H), 7.29 - 7.50 (m, 3H), 7.62 - 7.82 (m, 4H) ppm.

[0110] 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.

[0111] Example 6: Taste Evaluation - Comparison with MSG

[0112] Prepare an aqueous NaCl solution (0.5 wt%). Add to this base:

[0113] a) 30 ppm of Compound Ia (Sample 6a);

[0114] b) 200 ppm of MSG (Sample 6b, reference).

[0115] The tastes of both Samples 6a and 6b have been evaluated by 5 trained panelists. They were asked to rate the intensity of Sample 6a as different from Sample 6b and describe the overall effect. Typically, the following descriptors are used to describe the effect: umami, saltiness, bitterness, overall sweetness.

[0116] The taste of Sample 6a was described as umami, broth-like, and persistent. The umami at the bitterness level was marked slightly higher than the reference. Overall, Sample 6a was superior to Sample 6b.

[0117] Example 7: Taste Evaluation - Comparison with Other Derivatives

[0118] Prepare an aqueous NaCl solution (0.5 wt%). Add to this base:

[0119] a) 20 ppm of Compound Ia (Sample 7a);

[0120] b) 20 ppm of Compound Ib (Sample 7b);

[0121] c) 20 ppm of Compound Ic (Sample 7c).

[0122] The tastes of the three samples 7a, 7b, and 7c have been evaluated by 5 trained panelists.

[0123] Compared with Sample 7a, the taste of Sample 7b was described as more umami, stronger, more persistent, sweeter, but with an off-odor, animal-like, floral sweetness.

[0124] The taste of Sample 7c was described as more umami and fresher umami than Sample 7a.

[0125] Example 8: Taste Evaluation of Amide Ester Analogs

[0126] Prepare an aqueous solution of NaCl (0.5 wt%) and MSG (0.05 wt%). Add to this base:

[0127] a) A mixture of 20 ppm of compounds (Id + Ie) in a ratio of 1:2 (Sample 8a);

[0128] b) 20 ppm of compound If (Sample 8b).

[0129] A panel of four experienced tasters compared Samples 8a and 8b with the pure base.

[0130] Consistently, the panel found that Sample 8a was more umami than the base. Additionally, some bitterness was perceived.

[0131] Consistently, the panel found that Sample 8b was more umami than the base. The tasting was described as a pleasant taste experience.

Claims

1. Use of one or more compounds of formula (I) as an ingredient for imparting, enhancing, improving or modifying the umami taste of a consumer product composition, wherein X, Y = -NH- or -O-, with at least one of X or Y being -NH-, said compound being in the form of any one of its stereoisomers or a mixture thereof, wherein represents a carbon-carbon single bond or double bond, and one of the carbon-carbon double bonds is present at C2 or C3, the wavy bond represents an unspecified configuration of adjacent double bonds, wherein said one or more compounds of formula (I) are selected from (E)-N-(4-cinnamoylaminobutyl)-2-methylbut-2-enamide, (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamino)butyl)-2-methylbut-2-enamide, (E)-4-methoxy-N-(4-(2-methylbut-2-enoylamino)butyl)benzamide, (E)-4-cinnamoylaminobutyl 2-methylbut-2-enoate, 4-cinnamoylaminobutyl 2-methylbut-3-enoate and 4-((E)-2-methylbut-2-enoylamino)butyl cinnamate.

2. An umami flavor composition, comprising: (i) one or more compounds of formula (I) as defined in claim 1; and (ii) one or more additional flavor ingredients.

3. A consumer product composition, comprising: (i) at least one compound of formula (I) as defined in claim 1 or an umami flavor composition as defined in claim 2; and (ii) a product base.

4. A method for providing a consumer product composition having an umami taste, said method comprising the step of adding one or more compounds of formula (I) to a consumer product composition, wherein X, Y = -NH- or -O-, with at least one of X or Y being -NH-, said compound being in the form of any one of its stereoisomers or a mixture thereof, wherein represents a carbon-carbon single bond or double bond, provided that one of the dashed lines represents a double bond and the other represents a single bond, the wavy bond represents an unspecified configuration of adjacent double bonds, wherein said one or more compounds of formula (I) are selected from (E)-N-(4-cinnamoylaminobutyl)-2-methylbut-2-enamide, (E)-N-(4-((E)-3-(4-methoxyphenyl)acrylamino)butyl)-2-methylbut-2-enamide, (E)-4-methoxy-N-(4-(2-methylbut-2-enoylamino)butyl)benzamide, (E)-4-cinnamoylaminobutyl 2-methylbut-2-enoate, 4-cinnamoylaminobutyl 2-methylbut-3-enoate and 4-((E)-2-methylbut-2-enoylamino)butyl cinnamate.

5. A compound of formula (I) wherein X, Y = -NH- or -O-, with at least one of X or Y being -NH-, said compound being in the form of any one of its stereoisomers or a mixture thereof, wherein represents a carbon-carbon single bond or double bond, and one of the carbon-carbon double bonds is present at C2 or C3, the wavy bond represents an unspecified configuration of adjacent double bonds, The compound of formula (I) is selected from (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 2-methylbut-2-enoate, 4-cinnamamidobutyl 2-methylbut-3-enoate, and 4-((E)-2-methylbut-2-enamido)butyl cinnamate.

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