Methods of modifying or imparting taste using organic compounds

Abstract

A method of imparting to, or modifying in, a comestible product, umami taste, including the addition to a comestible product base of at least one compound of formula (I) ##STR00001##
wherein one of X.sub.1, X.sub.2, or X.sub.3 is selected from the group consisting of S, N and O and the remaining two are CH.sub.2; and A is selected from ##STR00002##
in which R.sub.1, R.sub.2, R.sub.3, R.sub.4 R.sub.5, R.sub.6 are independently selected from the group consisting of H, methyl, ethyl, propyl, OH, OMe, OEt, COOH, COOR.sub.7, in which R.sub.7 is selected from linear or branched C.sub.1-C.sub.7 alkyl, and CONR.sub.8R.sub.9, in which R.sub.8 and R.sub.9 are independently selected from hydrogen and straight or branched C.sub.1-C.sub.4 alkyl; or any two adjacent substituents R.sub.2-R.sub.6 together form a ring of 5 or 6 members; and n is 1 or 0.

Claims

1. A method of imparting to, or modifying in, a comestible product, umami taste comprising the addition to a comestible product base of at least one compound of formula (I) ##STR00021## wherein one of X.sub.1, X.sub.2, or X.sub.3 is selected from the group consisting of S, N and O and the remaining two are CH.sub.2; and A is selected from ##STR00022## in which R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 are independently selected from the group consisting of H, methyl, ethyl, propyl, OH, OMe, OEt, COOH, COOR.sub.7, in which R.sub.7 is selected from linear C.sub.1-C.sub.7 alkyl, branched C.sub.3-C.sub.7 alkyl, and CONR.sub.8R.sub.9, in which R.sub.8 and R.sub.9 are independently selected from hydrogen, straight C.sub.1-C.sub.4 alkyl, and branched C.sub.3-C.sub.4 alkyl; or any two adjacent substituents R.sub.2-R.sub.6 together form a ring of 5 or 6 members; and n is 1 or 0.

2. The method according to claim 1, in which one of X.sub.1, X.sub.2, or X.sub.3 is S and the remaining two are CH.sub.2.

3. The method according to claim 1, in which X.sub.1 is S, and, X.sub.2 and X.sub.3 are CH.sub.2.

4. The method according to claim 1, in which X.sub.2 is S, and, X.sub.1 and X.sub.3 are CH.sub.2.

5. The method according to claim 1, in which A is ##STR00023## in which R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 are independently selected from the group consisting of H, methyl, ethyl, propyl, OH, OMe, OEt, COOH, COOR.sub.7, in which R.sub.7 is selected from linear C.sub.1-C.sub.7 alkyl, branched C.sub.3-C.sub.7 alkyl, and CONR.sub.8R.sub.9, in which R.sub.8 and R.sub.9 are independently selected from hydrogen, straight C.sub.1-C.sub.4 alkyl, and branched C.sub.3-C.sub.4 alkyl; or any two adjacent substituents R.sub.2-R.sub.6 together form a ring of 5 or 6 members; and n is 1 or 0.

6. The method according to claim 1, in which X.sub.1 is S, and, X.sub.2 and X.sub.3 are CH.sub.2, and A is ##STR00024## in which R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 are independently selected from the group consisting of H, methyl, ethyl, propyl, OH, OMe, OEt, COOH, and COOR.sub.7, in which R.sub.7 is selected from linear C.sub.1-C.sub.7 alkyl and branched C.sub.3-C.sub.7 alkyl, and n is 0.

7. The method according to claim 1, in which the compound of formula (I) is selected from the group consisting of: 2-(2-(Phenylthio)ethyl)pyridine, 2-(2-(Phenylthio)ethyl)pyridine hydrochloride, Methyl 4-((2-(pyridin-2-yl)ethyl)thio) benzoate hydrochloride, 2-(2-(p-tolylthio)ethyl)pyridine hydrochloride, 2-(2-(o-tolylthio) ethyl)pyridine hydrochloride, 4-((2-(pyridin-2-yl)ethyl)thio)phenol, 2-((2-(pyridin-2-yl) ethyl)thio)phenol, 2-(2-((3-methoxyphenyl)thio)ethyl)pyridine, Methyl 2-((2-(pyridin-2-yl)ethyl)thio)benzoate hydrochloride, 3-((2-(pyridin-2-yl)ethyl)thio)phenol, 2-(2-(benzylthio)ethyl)pyridine, 2-(2-(m-Tolylthio)ethyl)pyridine hydrochloride, and 2-(2-((4-Methoxyphenyl)-thio)ethyl)pyridine hydrochloride.

8. The method according to claim 1, in which the compound of formula (I) is a salt.

9. The method according to claim 8, in which the compound of formula (I) is in the form of hydrochloride salt.

10. A method of imparting to, or modifying in, a flavour composition or comestible product, salt taste, comprising the addition to said flavour composition or comestible product of at least one compound of formula (I) ##STR00025## wherein one of X.sub.1, X.sub.2, or X.sub.3 is selected from the group consisting of S, N and O and the remaining two are CH.sub.2; and A is selected from ##STR00026## in which R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 are independently selected from the group consisting of H, methyl, ethyl, propyl, OH, OMe, OEt, COOH, COOR.sub.7, in which R.sub.7 is selected from linear C.sub.1-C.sub.7 alkyl, branched C.sub.3-C.sub.7 alkyl, and CONR.sub.8R.sub.9, in which R.sub.8 and R.sub.9 are independently selected from hydrogen, straight C.sub.1-C.sub.4 alkyl, and branched C.sub.3-C.sub.4 alkyl; or any two adjacent substituents R.sub.2-R.sub.6 together form a ring of 5 or 6 members; and n is 1 or 0.

11. A method of imparting to, or modifying in, a flavour composition or comestible product, a fruity, green, green pepper, tomato and/or bell pepper aroma, comprising the addition to said flavour composition or comestible product of at least one compound of formula (I) ##STR00027## wherein one of X.sub.1, X.sub.2, or X.sub.3 is selected from the group consisting of S, N and O and the remaining two are CH.sub.2; and A is selected from ##STR00028## in which R.sub.2, R.sub.3, R.sub.4 R.sub.5, R.sub.6 are independently selected from the group consisting of H, methyl, ethyl, propyl, OH, OMe, OEt, COOH, COOR.sub.7, in which R.sub.7 is selected from linear C.sub.1-C.sub.7 alkyl, branched C.sub.3-C.sub.7 alkyl, and CONR.sub.8R.sub.9, in which R.sub.8 and R.sub.9 are independently selected from hydrogen, straight C.sub.1-C.sub.4 alkyl, and branched C.sub.3-C.sub.4 alkyl; or any two adjacent substituents R.sub.2-R.sub.6 together form a ring of 5 or 6 members; and n is 1 or 0.

12. A method of imparting to, or modifying in, a flavour composition or comestible product, a kokumi sensation, comprising the addition to said flavour composition or comestible product of at least one compound of formula (I) ##STR00029## wherein one of X.sub.1, X.sub.2, or X.sub.3 is selected from the group consisting of S, N and O and the remaining two are CH.sub.2; and A is selected from ##STR00030## in which R.sub.2, R.sub.3, R.sub.4 R.sub.5, R.sub.6 are independently selected from the group consisting of H, methyl, ethyl, propyl, OH, OMe, OEt, COOH, COOR.sub.7, in which R.sub.7 is selected from linear C.sub.1-C.sub.7 alkyl, branched C.sub.3-C.sub.7 alkyl, and CONR.sub.8R.sub.9, in which R.sub.8 and R.sub.9 are independently selected from hydrogen, straight C.sub.3-C.sub.7 alkyl, and branched C.sub.3-C.sub.4 alkyl; or any two adjacent substituents R.sub.2-R.sub.6 together form a ring of 5 or 6 members; and n is 1 or 0.

13. The method according to claim 1, in which the at least one compound of formula (I) is added in a concentration of from 0.01 ppm to 500 ppm by weight based on the weight of the comestible product.

14. The method according to claim 10, in which the at least one compound of formula (I) is added in a concentration of from 0.01 ppm to 500 ppm by weight based on the weight of the comestible product, or at a concentration of 0.01% to 99.9% by weight of flavour components of the flavour composition.

15. The method according to claim 11, in which the at least one compound of formula (I) is added in a concentration of from 0.01 ppm to 500 ppm by weight based on the weight of the comestible product, or at a concentration of 0.01% to 99.9% by weight of flavour components of the flavour composition.

16. The method according to claim 12, in which the at least one compound of formula (I) is added in a concentration of from 0.01 ppm to 500 ppm by weight based on the weight of the comestible product, or at a concentration of 0.01% to 99.9% by weight of flavour components of the flavour composition.

Description

EXAMPLE 1: 2-(2-(PHENYLTHIO)ETHYL)PYRIDINE (CAS: 21070-71-3)

(1) ##STR00008##

(2) Benzenethiol (4.66 ml, 45.4 mmol) was added to Water (20 ml) followed by 2-vinylpyridine (4.89 ml, 45.4 mmol) and the contents were stirred overnight at room temperature (rt). The next day the product was extracted with ethyl acetate (100 ml). The organic layer was dried (Na.sub.2SO.sub.4), filtered and concentrated providing an oil. The crude oil was purified by column chromatography on SiO.sub.2 using a gradient of 100% hexane to 50:50 hexane:EtOAc providing the desired 2-(2-(phenylthio)ethyl)pyridine (8.2 g, 84% yield) as a clear oil. .sup.1H NMR (300 MHz, d.sub.6-DMSO, ppm) 3.019 (t, J=7 Hz, 2H), 3.34 (t, J=7 Hz, 2H), 7.08-7.40 (m, 7H), 7.66-7.71 (m, 1H), 8.49-8.51 (m, 1H); .sup.13C NMR (75 MHz, d.sub.6-DMSO, ppm) 31.5, 36.8, 121.6, 123.1, 125.6, 128.0, 129.0, 136.1, 136.4, 149.0, 159.2; GC/MS calculated for C.sub.13H.sub.13NS 215, observed 215.

EXAMPLE 2: 2-(2-(PHENYLTHIO)ETHYL)PYRIDINE HYDROCHLORIDE (CAS: 21070-72-4)

(3) ##STR00009##

(4) A portion of 2-(2-(phenylthio)ethyl)pyridine from example 1 was dissolved in ether and treated with HCl gas resulting in a sticky oil. Scratching the walls of the vial with a metal spatula induced crystallization providing the desired 2-(2-(phenylthio)ethyl)-pyridine hydrochloride as a white solid. The ether was removed by filtration and the white solid was dried overnight in a vacuum oven at 40 C. .sup.1H NMR (300 MHz, d.sub.6-DMSO, ppm) 3.38 (t, J=7 Hz, 2H), 3.50-3.55 (m, 2H), 7.16-7.22 (m, 1H), 7.27-7.39 (m, 4H), 7.84-7.89 (m, 1H), 7.96 (d, J=8 Hz, 1H), 8.75-8.78 (m, 1H); .sup.13C NMR (75 MHz, d.sub.6-DMSO, ppm) 30.7, 32.6, 124.9, 126.0, 127.3, 128.4, 129.1, 134.9, 141.5, 145.2, 154.6.

EXAMPLE 3: METHYL 4-((2-(PYRIDIN-2-YL)ETHYL)THIO)BENZOATE HYDROCHLORIDE (CAS: 298217-38-6)

(5) ##STR00010##

(6) Methyl 4-mercaptobenzoate (1 g, 5.94 mmol) was added to a 20 ml vial followed by Water (2.62 ml) and 2-vinylpyridine (0.641 ml, 5.94 mmol). The mixture was stirred overnight. The next day, the reaction mixture was diluted with ethyl acetate (10 ml) and passed through a Chem Elut extraction cartridge (Varian). The cartridge was washed several times with EtOAc. The dried theyl acetate and rinsings were collected in a 100 ml round bottom flask. The solvent was concentrated producing a crude cream colored solid. A TLC on silica gel using 50:50 hexane:EtOAc showed a single spot with an Rf of 0.8. The solid was dissolved in dichloromethane and chromatographed on SiO.sub.2 using a gradient of 100% hexane to 50:50 hexane:EtOAc. The product containing fractions were concentrated and the purified product was dissolved in ether and HCl gas was bubbled through. This generated a white, sticky oil that solidified into a white solid, when the vial was scratched with a spatula. The white solid was dried overnight at 40 C. in a vacuum oven providing the desired methyl 4-((2-(pyridin-2-yl)ethyl)thio)benzoate hydrochloride as a white solid (1.53 g, 83% yield). .sup.1H NMR (300 MHz, d.sub.6-DMSO, ppm) 3.43 (t, J=7 Hz, 2H), 3.62 (t, J=7 Hz, 2H), 3.83 (s, 3H), 7.47-7.51 (m, 2H), 7.83-7.91 (m, 3H), 8.00 (d, J=8 Hz, 1H), 8.47 (td, J.sub.1=8 Hz, J.sub.2=2 Hz, 1H), 8.78-8.80 (m, 1H); .sup.13C NMR (75 MHz, d.sub.6-DMSO, ppm) 29.4, 32.3, 52.0, 125.0, 126.3, 126.5, 127.3, 129.6, 141.6, 142.5, 145.3, 154.4, 165.8; GC/MS (Free base) calculated for C.sub.15H.sub.15NO.sub.2S 273, observed 273.

EXAMPLE 4: 2-(2-(P-TOLYLTHIO)ETHYL)PYRIDINE HYDROCHLORIDE (CAS: 109845-78-5)

(7) ##STR00011##

(8) 4-Methylbenzenethiol (0.738 g, 5.94 mmol) was added to a 20 ml vial followed by Water (2.62 ml) and 2-vinylpyridine (0.641 ml, 5.94 mmol). The mixture was stirred overnight. The next day, the reaction mixture was diluted with ethyl acetate (10 ml) and passed through a Chem Elut extraction cartridge (Varian). The cartridge was washed several times with EtOAc and the dried reaction and rinsings were collected in a 100 ml round bottom flask. The solvent was concentrated producing a crude cream colored solid. A TLC on silica gel using 50:50 hexane:EtOAc showed a single spot with an Rf of 0.8. The solid was dissolved in dichloromethane and chromatographed on SiO.sub.2 using a gradient of 100% hexane to 50:50 hexane:EtOAc. The resulting product was dissolved in ether and treated with HCl gas. This produced, after scratching with a spatula and vacuum oven drying at 40 C., the desired 2-(2-(p-tolylthio)-ethyl)pyridine hydrochloride as a white solid (1.26 g, 80% yield). .sup.1H NMR (300 MHz, d.sub.6-DMSO, ppm) 2.26 (s, 3H), 3.30-3.35 (m, 2H), 3.44-3.49 (m, 2H), 7.11-7.14 (m, 2H), 7.26-7.30 (m, 2H), 7.84-7.89 (m, 1H), 7.93 (d, J=8 Hz, 1H), 8.44 (td, J.sub.1=8 Hz, J.sub.2=2 Hz, 1H), 8.74-8.77 (m, 1H); .sup.13C NMR (75 MHz, d.sub.6-DMSO, ppm) 20.5, 31.4, 32.8, 124.9, 127.3, 129.3, 129.8, 131.1, 135.8, 141.6, 145.2, 154.7; GC/MS (Free base) calculated for C.sub.14H.sub.15NS 229, observed 229.

EXAMPLE 5: 2-(2-(O-TOLYLTHIO)ETHYL)PYRIDINE HYDROCHLORIDE (CAS: 109846-70-0)

(9) ##STR00012##

(10) 2-Methylbenzenethiol (1 g, 8.05 mmol) was added to a 20 ml vial followed by Water (3.5 ml) and 2-vinylpyridine (0.846 g, 8.05 mmol). The mixture was stirred overnight. The next day, the reaction mixture was diluted with ethyl acetate (10 ml) and passed through a Chem Elut extraction cartridge (Varian). The cartridge was washed several times with EtOAc and the dried reaction and rinsings were collected in a 100 ml round bottom flask. The solvent was concentrated producing a crude cream colored solid. A TLC on silica gel using 50:50 hexane:EtOAc showed a single spot with an Rf of 0.8. The solid was dissolved in dichloromethane and chromatographed on SiO.sub.2 using a gradient of 100% hexane to 50:50 hexane:EtOAc. The resulting product was dissolved in ether and treated with HCl gas. This produced, after scratching with a spatula and vacuum oven drying at 40 C., the desired 2-(2-(p-tolylthio)-ethyl)pyridine hydrochloride as a white solid (1.19 g, 56% yield). .sup.1H NMR (300 MHz, d.sub.6-DMSO, ppm) 2.24 (s, 3H), 3.34-3.40 (m, 2H), 3.47-3.53 (m, 2H), 7.09-7.14 (m, 1H), 7.17-7.21 (m, 2H), 7.40-7.43 (m, 1H), 7.81-7.86 (m, 1H), 7.93 (d, J=8 Hz, 1H), 8.41 (td, J.sub.1=8 Hz, J.sub.2=2 Hz, 1H), 8.75-8.78 (m, 1H); .sup.13C NMR (75 MHz, d.sub.6-DMSO, ppm) 19.8, 30.2, 32.8, 124.7, 125.7, 126.6, 126.9, 127.5, 130.1, 134.3, 136.4, 142.1, 144.6, 155.0; GC/MS (Free base) calculated for C.sub.14H.sub.15NS 229, observed 229.

EXAMPLE 6: 4-((2-(PYRIDIN-2-YL)ETHYL)THIO)PHENOL (CAS: 1183541-70-9)

(11) ##STR00013##

(12) 4-Mercaptophenol (0.749 g, 5.94 mmol) was added to Water (2.62 ml) followed by 2-vinylpyridine (0.641 ml, 5.94 mmol) and the mixture was stirred overnight. The next day, the reaction mixture was diluted with ethyl acetate (10 ml) and passed through a Chem Elut extraction cartridge (Varian). The cartridge was washed several times with EtOAc and the dried reaction and rinsings were collected in a 100 ml round bottom flask. The solvent was concentrated producing a crude oil. The crude oil was dissolved in dichloromethane and chromatographed on SiO.sub.2 using a gradient of 100% hexane to 80:20 hexane:EtOAc providing the desired product (1.07 g, 78% yield) as a white solid. .sup.1H NMR (300 MHz, d.sub.6-DMSO, ppm) 2.92 (t, J=7 Hz, 2H), 3.13-3.36 (m, 2H), 6.73-6.78 (m, 2H), 7.18-7.27 (m, 4H), 7.68 (td, J.sub.1=8 Hz, J.sub.2=2 Hz, 1H), 8.46-8.48 (m, 1H), 9.57 (s, 1H); .sup.13C NMR (75 MHz, d.sub.6-DMSO, ppm) 34.3, 37.2, 116.1, 121.5, 123.1, 123.4, 133.0, 136.4, 149.0, 156.8, 159.4; GC/MS calculated for C.sub.13H.sub.13NOS 231, observed 231.

EXAMPLE 7: 2-((2-(PYRIDIN-2-YL)ETHYL)THIO)PHENOL (CAS: 1247529-36-7)

(13) ##STR00014##

(14) 2-Mercaptophenol (0.749 g, 5.94 mmol) was added to Water (2.62 ml) followed by 2-vinylpyridine (0.641 ml, 5.94 mmol) and the mixture was stirred overnight. The next day, the reaction mixture was diluted with ethyl acetate (10 ml) and passed through a Chem Elut extraction cartridge (Varian). The cartridge was washed several times with EtOAc and the dried reaction and rinsings were collected in a 100 ml round bottom flask. The solvent was concentrated producing a crude oil. The crude oil was dissolved in dichloromethane and chromatographed on SiO.sub.2 using a gradient of 100% hexane to 80:20 hexane:EtOAc providing the desired product (1.15 g, 84% yield) as a white solid. .sup.1H NMR (300 MHz, d.sub.6-DMSO, ppm) 2.98 (t, J=7 Hz, 2H), 3.19-3.25 (m, 2H), 6.77-6.85 (m, 2H), 7.03-7.08 (m, 1H), 7.20-7.30 (m, 3H), 7.71 (td, J.sub.1=8 Hz, J.sub.2=2 Hz, 1H), 8.49-8.51 (m, 1H), 9.83 (s, 1H); .sup.13C NMR (75 MHz, d.sub.6-DMSO, ppm) 30.7, 36.8, 115.0, 119.6, 121.58, 121.6, 123.1, 127.1, 129.6, 136.5, 148.9, 155.5, 159.4; GC/MS calculated for C.sub.13H.sub.13NOS 231, observed 231.

EXAMPLE 8: 2-(2-((3-METHOXYPHENYL)THIO)ETHYL)PYRIDINE

(15) ##STR00015##

(16) 3-Methoxybenzenethiol (0.833 g, 5.94 mmol) was added to Water (2.62 ml) followed by 2-vinylpyridine (0.641 ml, 5.94 mmol) and the mixture was stirred overnight. The next day, the reaction mixture was diluted with ethyl acetate (10 ml) and passed through a Chem Elut extraction cartridge (Varian). The cartridge was washed several times with EtOAc and the dried reaction and rinsings were collected in a 100 ml round bottom flask. The solvent was concentrated producing a crude oil. The crude oil was dissolved in dichloromethane and chromatographed on SiO.sub.2 using a gradient of 100% hexane to 80:20 hexane:EtOAc providing the desired product (1.14 g, 78% yield) as a clear oil. .sup.1H NMR (300 MHz, d.sub.6-DMSO, ppm) 3.03 (t, J=7 Hz, 2H), 3.32-3.37 (m, 2H), 3.75 (s, 3H), 6.75 (ddd, J.sub.1=8 Hz, J.sub.2=2 Hz, 1 Hz, 1H), 6.87-6.92 (m, 2H), 7.20-7.30 (m, 3H), 7.70 (ddd, J.sub.1=8 Hz, J.sub.2=2 Hz, 1H), 8.49-8.51 (m, 1H); .sup.13C NMR (75 MHz, d.sub.6-DMSO, ppm) 31.3, 36.8, 55.1, 111.4, 113.0, 119.9, 121.6, 123.1, 129.9, 136.4, 137.5, 149.0, 159.2, 159.6; GC/MS calculated for C.sub.14H.sub.15NOS 245, observed 245.

EXAMPLE 9: METHYL 2-((2-(PYRIDIN-2-YL)ETHYL)THIO)BENZOATE HYDROCHLORIDE

(17) ##STR00016##

(18) Methyl 2-mercaptobenzoate (0.999 g, 5.94 mmol) was added to Water (2.62 ml) followed by 2-vinylpyridine (0.641 ml, 5.94 mmol) and the mixture was stirred overnight. The next day, the reaction mixture was diluted with ethyl acetate (10 ml) and passed through a Chem Elut extraction cartridge (Varian). The cartridge was washed several times with EtOAc and the dried reaction and rinsings were collected in a 100 ml round bottom flask. The solvent was concentrated producing a crude oil. The crude oil was dissolved in dichloromethane and chromatographed on SiO.sub.2 using a gradient of 100% hexane to 50:50 hexane:EtOAc. The resulting product was dissolved in ether and treated with HCl gas. This produced, after scratching with a spatula and vacuum oven drying at 40 C., the desired product as a white solid (1.45 g, 79% yield). .sup.1H NMR (300 MHz, d.sub.6-DMSO, ppm) 3.41-3.56 (m, 4H), 3.82 (s, 3H), 7.25-7.31 (m, 1H), 7.55-7.66 (m, 2H), 7.86-7.93 (m, 2H), 8.03 (d, J=8 Hz, 1H), 8.50 (ddd, J.sub.1=8 Hz, J.sub.2=2 Hz, 1H), 8.80-8.82 (m, 1H); .sup.13C NMR (75 MHz, d.sub.6-DMSO, ppm) 29.6, 31.8, 52.1, 124.5, 125.0, 126.3, 127.3, 127.6, 130.7, 132.8, 139.2, 141.5, 145.5, 154.6, 166.0; GC/MS (Free base) calculated for C15H15NO.sub.2S 273, observed 273.

EXAMPLE 10: 3-((2-(PYRIDIN-2-YL)ETHYL)THIO)PHENOL

(19) ##STR00017##

(20) 3-mercaptophenol (0.749 g, 5.94 mmol) was added to Water (2.62 ml) followed by 2-vinylpyridine (0.641 ml, 5.94 mmol) and the mixture was stirred overnight. The next day, the reaction mixture was diluted with ethyl acetate (10 ml) and passed through a Chem Elut extraction cartridge (Varian). The cartridge was washed several times with EtOAc and the dried reaction and rinsings were collected in a 100 ml round bottom flask. The solvent was concentrated producing a crude oil. The crude oil was dissolved in dichloromethane and chromatographed on SiO.sub.2 using a gradient of 100% hexane to 80:20 hexane:EtOAc providing the desired product (0.82 g, 60% yield) as a clear oil.

(21) .sup.1H NMR (300 MHz, d.sub.6-DMSO, ppm) 3.02 (t, J=7 Hz, 2H), 3.27-3.32 (m, 2H), 6.57-6.61 (m, 1H), 6.74-6.77 (m, 2H), 7.08-7.14 (m, 1H), 7.19-7.29 (m, 2H), 7.70 (ddd, J.sub.1=8 Hz, J.sub.2=2 Hz, 1H), 8.49-8.51 (m, 1H), 9.53 (s, 1H); .sup.13C NMR (75 MHz, d.sub.6-DMSO, ppm) 31.4, 36.8, 112.8, 114.5, 118.5, 121.6, 123.1, 129.9, 136.4, 137.0, 149.0, 157.8, 159.2; GC/MS calculated for C.sub.13H.sub.13NOS 231, observed 231.

EXAMPLE 11: 2-(2-(BENZYLTHIO)ETHYL)PYRIDINE (CAS: 31932-68-0)

(22) ##STR00018##

(23) Phenylmethanethiol (0.697 ml, 5.94 mmol) was added to Water (2.62 ml) followed by 2-vinylpyridine (0.641 ml, 5.94 mmol) and the mixture was stirred overnight. The next day, the reaction mixture was diluted with ethyl acetate (10 ml) and passed through a Chem Elut extraction cartridge (Varian). The cartridge was washed several times with EtOAc and the dried reaction and rinsings were collected in a 100 ml round bottom flask. The solvent was concentrated producing a crude oil. The crude oil was dissolved in dichloromethane and chromatographed on SiO.sub.2 using a gradient of 100% hexane to 80:20 hexane:EtOAc providing the desired product (0.76 g, 56% yield) as a clear oil.

(24) .sup.1H NMR (300 MHz, d.sub.6-DMSO, ppm) 2.73-2.79 (m, 2H), 2.96 (t, J=7 Hz, 2H), 3.74 (s, 2H), 7.18-7.28 (m, 3H), 7.29-7.32 (m, 4H), 7.68 (ddd, J.sub.1=8 Hz, J.sub.2=2 Hz, 1H), 8.46-8.49 (m, 1H); .sup.13C NMR (75 MHz, d.sub.6-DMSO, ppm) 30.2, 35.0, 37.2, 121.5, 123.0, 126.7, 128.3, 128.8, 136.3, 138.6, 149.0, 159.7; GC/MS calculated for C.sub.14H.sub.15NS 229, observed 229.

EXAMPLE 12: 2-(2-(M-TOLYLTHIO)ETHYL)PYRIDINE HYDROCHLORIDE

(25) ##STR00019##

(26) 3-Methylbenzenethiol (0.707 ml, 5.94 mmol) was added to water (2.62 ml) followed by 2-vinylpyridine (0.641 ml, 5.94 mmol) and the mixture was stirred overnight. The next day, the reaction mixture was diluted with ethyl acetate (10 ml) and passed through a Chem Elut extraction cartridge (Varian). The cartridge was washed several times with EtOAc and the dried reaction and rinsings were collected in a 100 ml round bottom flask. The solvent was concentrated producing a crude oil. The crude oil was dissolved in dichloromethane and chromatographed on SiO.sub.2 using a gradient of 100% hexane to 50:50 hexane:EtOAc. The resulting product was dissolved in ether and treated with HCl gas. This produced, after scratching with a spatula and vacuum oven drying at 40 C., the desired product as a white solid (0.93 g, 59% yield). .sup.1H NMR (300 MHz, d.sub.6-DMSO, ppm) 2.27 (s, 3H), 3.35-3.40 (m, 2H), 3.49-3.54 (m, 2H), 6.97-7.01 (m, 1H), 7.13-7.21 (m, 3H), 7.87 (ddd, J.sub.1=7 Hz, J.sub.2=6 Hz, J.sub.3=1 Hz, 1H), 7.96 (d, J=8 Hz, 1H), 8.46 (ddd, J.sub.1=8 Hz, J.sub.2=1 Hz, 1H), 8.75-8.77 (m, 1H); .sup.13C NMR (75 MHz, d.sub.6-DMSO, ppm) 20.8, 30.7, 32.7, 125.0, 125.5, 126.8, 127.4, 128.9, 134.6, 138.5, 141.4, 145.4, 154.5; GC/MS (Free base) calculated for C.sub.14H.sub.15NS 229, observed 229.

EXAMPLE 13: 2-(2-((4-METHOXYPHENYL)THIO)ETHYL)PYRIDINE HYDROCHLORIDE (CAS: 261360-83-2)

(27) ##STR00020##

(28) 4-Methoxybenzenethiol (0.833 g, 5.94 mmol) was added to Water (2.62 ml) followed by 2-vinylpyridine (0.641 ml, 5.94 mmol) and the mixture was stirred overnight. The next day, the reaction mixture was diluted with ethyl acetate (10 ml) and passed through a Chem Elut extraction cartridge (Varian). The cartridge was washed several times with EtOAc and the dried reaction and rinsings were collected in a 100 ml round bottom flask. The solvent was concentrated producing a crude oil. The crude oil was dissolved in dichloromethane and chromatographed on SiO.sub.2 using a gradient of 100% hexane to 50:50 hexane:EtOAc. The resulting product was dissolved in ether and treated with HCl gas. This produced, after scratching with a spatula and vacuum oven drying at 40 C., the desired product as a white solid (0.64 g, 38% yield). .sup.1H NMR (300 MHz, d.sub.6-DMSO, ppm) 3.29-3.34 (m, 2H), 3.38-3.43 (m, 2H), 3.73 (s, 3H), 6.86-6.91 (m, 2H), 7.32-7.37 (m, 2H), 7.85-7.90 (m, 1H), 7.94 (d, J=8 Hz, 1H), 8.46 (ddd, J.sub.1=8 Hz, J.sub.2=1 Hz, 1H), 8.75-8.76 (m, 1H); .sup.13C NMR (75 MHz, d.sub.6-DMSO, ppm) 32.7, 32.9, 55.2, 114.8, 124.6, 125.0, 127.4, 132.5, 141.3, 145.4, 154.6, 158.5; GC/MS (Free base) calculated for C.sub.14H.sub.15NOS 245, observed 245.

EXAMPLE 14: TASTE EVALUATION IN WATER

(29) A one percent cut of each compound of Examples 1-13 was prepared first. The hydrochloride salts were cut directly into water, while the free base examples were cut into ethanol. Next, 100 ml of a 1 ppm, 10 ppm and 20 ppm solution were prepared. The 1 ppm standards were prepared by addition of 0.0126 ml (cut in ethanol) or 0.01 ml (cut in water) to an amber bottle followed by dilution to 100 g total sample weight using water. The 10 and 20 ppm solutions were prepared similarly, but using 0.126 ml ethanol/0.1 ml water or 0.252 ml ethanol/0.2 ml water of the 1% cuts respectively. Next, the samples were evaluated by a panel of trained tasters. The data from these taste sessions are presented in Table I.

(30) TABLE-US-00001 TABLE I Taste evaluation in water Conc. Ex. (ppm) taste aroma 1 1 weak to moderate umami green 1 10 moderate umami, very weak: bitter, very weak green astringent, salty 1 20 strong umami, very weak bitter, weak metallic Green, tomato, bell pepper 2 1 weak umami, very weak astringent green 2 10 moderate umami, very weak: salty, bitter, green metallic, astringent 2 20 moderate umami, weak: salty, bitter, astringent green 3 1 weak to moderate umami, very weak: bitter, metallic, astringent 3 10 moderate umami, weak: bitter, metallic, bloody metallic astringent, 3 20 moderate to strong umami, weak: bitter, bloody metallic metallic 4 1 very weak: umami, bitter, astringent 4 10 weak: umami, bitter, astringent, very weak green metallic 4 20 Weak: umami, bitter, metallic, sour, astringent green 5 1 weak bitter, astringent, very weak metallic green pepper 5 10 weak umami, very weak bitter green pepper 5 20 weak umami, very weak: bitter, astringent green pepper 6 1 very weak: umami, astringent green 6 10 weak: umami, bitter, astringent, very weak Green, fruity metallic 6 20 weak: umami, bitter, astringent, very weak Green, fruity metallic 7 1 very weak: umami, salty, weak bitter Green pepper 7 10 weak to moderate umami, weak: bitter, metallic, Green pepper very weak salty, 7 20 Weak to moderate umami, weak bitter, very Green pepper weak salty, metallic, astringent 8 1 very weak metallic, weak astringent Green pepper, beany 8 10 weak: umami, astringent, very weak: bitter, Green pepper metallic, 8 20 weak: umami, very weak: bitter, metallic Green pepper 9 1 weak: umami, astringent, very weak: salty, bitter 9 10 moderate umami,, weak: salty, astringent, very weak: bitter, metallic 9 20 moderate umami, weak: salty, astringent, tingling, very weak: salivating, metallic 10 1 very weak bitter green 10 10 weak: umami, metallic, very weak: bitter, astringent 10 20 weak: umami, astringent, bitter, very weak: vegetable salty, metallic 11 1 weak umami, very weak astringent phenolic 11 10 weak umami, very weak astringent Phenolic, spicy 11 20 moderate to strong umami, very weak bitter, Phenolic, spicy weak astringent 12 1 weak: umami, astringent, very weak salty 12 10 moderate umami, weak: salty, astringent 12 20 moderate to strong umami, weak: salty, astringent 13 1 Weak umami, very weak bitter, astringent 13 10 Moderate to strong umami, very weak: bitter, salty 13 20 Strong umami, very weak bitter pyrazine

EXAMPLE 15: FLAVOR APPLICATION EXAMPLES

(31) Umami evaluations were done in dry noodle seasoning, chicken broth, retorted chicken broth, cheese sauce and salted potato chip applications. Each application was prepared using MSG, the experimental umami tastant and a blank which contained neither MSG nor the experimental umami tastant. Next, using a bench-top tasting panel (consisting of 7 to 14 panelists), panelists were asked to record the sensory attribute differences between the control (blank), the MSG application and the application containing the experimental umami tastant. These sensory attributes include umami, saltiness, bitterness, off-notes, mouth feel attribute, lingering attribute and flavor profile differences.

(32) Noodle Seasoning Broth

(33) TABLE-US-00002 Ingredient % Salt 51.28 Sugar 11.49 Citric acid 0.1 Palm fat 1.54 Turmeric powder 0.21 Whey powder 15.38 Maltodextrin (DE10) 20.0 TOTAL 100

(34) Turmeric was plated on salt and palm fat and blended well. Next, the remaining ingredients were added and mixed until well blended. A concentration of 1.5% of the resulting mixture in hot water generated the noodle seasoning broth.

(35) The following three samples were tasted and compared.

(36) TABLE-US-00003 Ingredient % (by weight) Noodle Seasoning Broth 100 MSG 0.1 Noodle Seasoning Broth Balance to 100 Example 1 0.0001 Noodle Seasoning Broth Balance to 100

(37) Sensory Findings:

(38) The panelists ranked the umami strength of the noodle seasoning broth samples as follows: MSG>Example 1>Blank Noodle Seasoning. Some panelists noted a green pepper attribute in the Example 1 containing sample.

(39) Number of panelists: 11

(40) Number of panelists who noted green pepper offnote: 2

EXAMPLE 16: CHICKEN BROTH

(41) TABLE-US-00004 Amount - Amount - Name base tasting sample Chicken Fat 10.12 g 0.25 g Salt 18.21 g 0.50 g Onion powder 0.81 g 0.02 g Ground turmeric 0.04 g 0.001 g Chicken broth powder 60.7 g 1.50 g Chicken broth powder 10.1 g 0.25 g Water 97.479 g

(42) Turmeric was plated on salt and chicken fat and blended well. Next, the remaining ingredients were added and mixed until well blended. A concentration of 2.5% of the resulting mixture in hot water (82 C. (180 F.)) generated the noodle seasoning broth.

(43) TABLE-US-00005 Ingredient % (by weight) Chicken Broth 100 MSG 0.1 Chicken Broth Balance to 100 Example 1 0.0002 Chicken Broth Balance to 100

(44) Sensory Findings:

(45) The panelists ranked the umami strength of the chicken broth samples as follows: MSG>Example 1>Blank Chicken Broth. Some panelists noted a green pepper/chili off-note attribute in the Example 1 containing sample.

(46) Number of panelists: 11

(47) Number of panelists who noted green pepper offnote: 3

EXAMPLE 17: RETORTED CHICKEN BROTH

(48) The chicken broth generated in Example 16 was transferred to a can and sealed. Prior to sealing one batch was treated with the compound of Example 1 (0.0002% by weight) and the other batch was canned without the ingredient generating a blank control sample. After sealing the cans, they were heated to 121 C. (250 F.) (under pressure) for 25 minutes, cooled to room temperature and then stored in the refrigerator for two weeks. Prior to tasting, the cans were opened and reheated to 65.5 C. (150 F.).

(49) TABLE-US-00006 Ingredient % (by weight) Retorted Chicken Broth 100 Example 1 0.0002 Retorted Chicken Broth Balance to 100

(50) Sensory Findings:

(51) The panelists thought that the retorted chicken broth sample containing example 1 had more umami than the control but had pepper off-notes.

(52) Number of panelists: 10

(53) Number of panelists who noted green pepper offnote: 4

EXAMPLE 18: CHEESE SAUCE

(54) TABLE-US-00007 Formula Weight Ingredients grams lbs % Maltodextrin 31.08 0.07 31.08% MF Starch 16.00 0.04 16.00% Cheese Powder 19.00 0.04 19.00% Nonfat dry milk 12.00 0.03 12.00% powder Shortening Powder 8.00 0.02 8.00% Whey, Sweet 6.00 0.01 6.00% Salt, Fine 2.70 0.01 2.70% Cream Powder 3.00 0.01 3.00% Sodium Phosphate 1.00 0.00 1.00% KCL 0.72 0.00 0.72% Annatto, LQ 0.20 0.00 0.20% Citric Acid 0.20 0.00 0.20% Lactic Acid 0.10 0.00 0.10% TOTALS 100.00 0.22 100.00%

(55) Annatto was plated on a mixture of salt, citric acid and lactic acid and blended well. Next, the remaining ingredients were added and mixed until well blended. The dry sauce mix was added to water to a concentration of 18% and cooked to boiling (100 C. (212 F.)).

(56) TABLE-US-00008 Ingredient % (by weight) Cheese Sauce 100 MSG 0.1 Cheese Sauce Balance to 100 Example 1 0.00025 Cheese Sauce Balance to 100

(57) Sensory Findings:

(58) The panelists ranked the umami strength of the cheese sauce samples as follows: MSG>Example 1>Blank Cheese Sauce. Some panelists noted a green pepper attribute in the Example 1 containing sample.

(59) Number of panelists: 14

(60) Number of panelists who noted green pepper offnote: 4

EXAMPLE 19: SALTED POTATO CHIPS

(61) One percent salt was added to a standard unsalted potato chip.

(62) TABLE-US-00009 Ingredient % (by weight) 1% salted potato chips 100 MSG 0.2 1% salted potato chips Balance to 100 Example 1 0.0001 1% salted potato chips Balance to 100 Example 1 0.0003 1% salted potato chips Balance to 100

(63) Sensory Findings:

(64) The panelists ranked the umami strength of the potato chip samples as follows: MSG>3 ppm Example 1>1 ppm Example 1>Blank Salted Chips. Some panelists noted a peppery attribute in the Example 1 containing samples.

(65) Number of panelists: 14

(66) Number of panelists who noted green pepper offnote: 2

EXAMPLE 20: RETORTED CHICKEN BROTH

(67) The procedure for the preparation of the retorted chicken broth is the same as in example 16. Compounds from Examples 3, 9, 10 and 13 were spiked individually into the chicken broth generating six samples, as described below.

(68) TABLE-US-00010 Ingredient % (by weight) Chicken Broth 100 MSG 0.20 Chicken Broth Balance to 100 Example 3 4 ppm Chicken Broth Balance to 100 Example 13 3 ppm Chicken Broth Balance to 100 Example 10 4 ppm Chicken Broth Balance to 100 Example 9 3 ppm Chicken Broth Balance to 100

(69) Sensory Findings:

(70) The panelists ranked the umami strength of the chicken broth retort samples as follows: MSG>3 ppm example 9>3 ppm Example 13>4 ppm Example 3>Blank retorted chicken broth>4 ppm Example 10. Some panelists noted a sweeter flavor profile with a build up of umami character for example 3. Example 13 had a slightly sweet/slightly bitter profile. Example 10 had a green pepper aroma and was slightly bitter. Example 9 possessed a sweet, full umami profile.

(71) Number of panelists: 9

EXAMPLE 21: BAIN MARIE (HOT WATER BATH) TEST WITH CHICKEN BROTH

(72) Chicken broth was prepared as previously described in example 15. Compounds from Examples 3, 9, 10 and 13 were added to the chicken broth in the concentrations described below and placed in a hot water bath (150 F.) for 4 hours prior to taste evaluation.

(73) TABLE-US-00011 Ingredient % (by weight) Chicken Broth 100 MSG 0.20 Chicken Broth Balance to 100 Example 3 3 ppm Chicken Broth Balance to 100 Example 13 2 ppm Chicken Broth Balance to 100 Example 10 3 ppm Chicken Broth Balance to 100 Example 9 2 ppm Chicken Broth Balance to 100

(74) Sensory Findings:

(75) The panelists ranked the umami strength of the Bain marie chicken broth samples as follows: MSG>2 ppm example 9>3 ppm Example 10=4 ppm Example 13>Blank chicken broth>3 ppm Example 3. Some panelists noted a bitter, limited umami flavor profile for example 3 in this application, while example 13 was described as mid/late umami with some late onset bitterness. Example 10 was described as having mid/late umami along with a slight bitterness and off notes. Example 9 was described as providing a boost in saltiness along with a strong, full umami taste profile.

(76) Number of panelists: 7

EXAMPLE 22: SALTED POTATO CHIPS

(77) The potato chips were prepared as previously described in example 19 and spiked with compounds from Examples 3, 9, 10 and 13 as described below.

(78) TABLE-US-00012 Ingredient % (by weight) 1% salted potato chips 100 MSG 0.2 1% salted potato chips Balance to 100 Example 3 10 ppm 1% salted potato chips Balance to 100 Example 13 10 ppm 1% salted potato chips Balance to 100 Example 10 6 ppm 1% salted potato chips Balance to 100 Example 9 10 ppm 1% salted potato chips Balance to 100

(79) Sensory Findings:

(80) The panelists ranked the umami strength of the potato chip samples as follows: 10 ppm Example 3>10 ppm Example 9>MSG>10 ppm Example 13>blank>6 ppm Example 10. Some panelists noted a slight to moderate level of umami along with strong salty profile for example 3. A good, salty, umami profile was described for example 13. Example 10 was described as having a nice salty, slight umami profile along with a slight offnote. Example 9 was described as better mouthfeel, slight to moderate umami with an overall clean profile.

(81) Number of panelists: 9

(82) Although the embodiments have been described in detail through the above description and the preceding examples, these examples are for the purpose of illustration only and it is understood that variations and modifications can be made by one skilled in the art without departing from the spirit and the scope of the disclosure. It should be understood that the embodiments described above are not only in the alternative, but can be combined.