Claims
- 1. Process for enhancing or improving animal, grilled, roasted and fatty flavour notes in foodstuffs, beverages and animal feeds which comprises the step of adding thereto from about 0.02 to about 20 parts per million by weight, based on the total weight of the said materials, of at least one of the compounds of formula ##STR5## wherein symbol R.sup.1 represents a hydrogen atom or a methyl radical and R.sup.2 stands for a lower alkyl radical containing from 1 to 6 carbon atoms.
- 2. The process of claim 1 wherein the foodstuff is meat, a meat imitating or a meat containing consumable material.
- 3. The process according to claim 1 wherein the compound is 2-methyl-4-acetyl-pyrimidine.
- 4. The process according to claim 1 wherein the compound is 2-methyl-4-propionyl-pyrimidine.
- 5. The process according to claim 1 wherein the compound is 4-isovaleryl-pyrimidine.
- 6. The process according to claim 1 wherein the compound is 2-methyl-4-isovaleryl-pyrimidine.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 227/77 |
Jan 1977 |
CHX |
|
BACKGROUND OF THE INVENTION
In the course of the last decade particularly great attention has been devoted by various research groups to the study of the flavour properties of heterocyclic compounds, viz. nitrogen containing heterocyclic compounds. Various pyrazines have been shown in the literature to have flavour implications and have been considered essential ingredients for the reconstitution of flavour compositions of different nature [see e.g.: Fenaroli's Handbook of Flavor Ingredients, CRC Press, Inc., Cleveland (1975), vol. II, p. 692 and ff.; United Kingdom Pat. Nos. 1,156,472, 1,156,475 and 1,156,484].
Certain nitrogen containing heterocyclic derivatives belonging to the class of pyridines, pyrroles as well as thiazoles have also been described as possessing useful gustative properties [see e.g.: United Kingdom Pat. Nos. 1,156,483, 1,156,482 and 1,156,485]. Up to now, however, no suggestion has been formulated as to the possibility of using pyrimidic compounds as flavouring ingredients.
It has now unexpectedly been found that the flavour and the taste of foodstuffs in general, beverages, animal feeds, pharmaceutical preparations and tobacco products can be altered by adding thereto a small but effective amount of at least one compound of formula (I).
A particularly preferred class of the said compounds include
Most of the above cited compounds are new and are defined by the abbreviation "n.c."
The new compounds cited above include those compounds of particular interests defined by the following formula (I') ##STR1## wherein either symbol R' represents a hydrogen atom and R.sup.2 stands for an isobutyl radical, or symbol R' represents a methyl radical and R.sup.2 stands for a methyl, an ethyl or an isobutyl radical.
One of the objects of the invention relates to a process for enhancing, improving or modifying the flavour properties of foodstuffs, beverages, animal feeds, pharmaceutical preparations and tobacco products, which process comprises the step of adding to said materials a small but effective amount of at least one of the compounds of formula (I). This invention relates further to a flavour composition which comprises having added thereto at least one of the compounds of formula (I).
More particularly, the invention provides a process for modifying the organoleptic properties of meat, meat imitating or meat containing consumable materials which process comprises adding to said materials at least one of the compounds of formula (I).
In their pure state the compounds of formula (I) develop gustative notes of various type, such as e.g. animal, grilled, roasted and fatty flavour notes. Their flavour character, sweetish and caramel-like, is reminiscent of the taste developed by meat. Typically, the compounds of formula (I) find a very useful application in the manufacture of flavour compositions destined to the aromatization of meat, meat imitating or meat substituting edible materials. However, it has to be understood that owing to their gustative properties the pyrimidines of formula (I) find a broad spectrum of utility and they can be employed in a wide range of materials such as e.g. coffee, chocolate, dairy products, yoghurts, confectionary and bakery materials.
Compounds (I) find also a useful application in the aromatization of tobacco and tobacco substitute products.
The proportions at which the said compounds can achieve interesting gustative effects vary within wide limits. Preferentially, these proportions are of from about 0.02 to about 20 ppm (parts per million) by weight based on the total weight of the material into which they are incorporated. These values, however, should not be interpreted restrictively and it should be understood by those skilled in the art that concentrations lower or higher than those indicated above may be used whenever it is desired to achieve special effects. It is moreover well known in the art that the concentrations of a given flavourant depend on the nature of the specific material it is desired to aromatize and on the nature of the coingredients in a given composition. Pyrimidines (I) can in fact be used as such, either by effecting a direct addition of them in their pure state or, more frequently, by adding them in the form of a solution in a current edible solvent, such as ethanol, dipropyleneglycol or triacetine, or in admixture with other flavour ingredients in the form of a flavour composition.
Pyrimidines (I) can be prepared by using conventional processes. The processes are illustrated in details in the following experimental section wherein temperatures are indicated in degrees centigrade and the abbreviations have the meaning common in the art.
4-Acetyl-pyrimidine, 4-propionyl-pyrimidine and 4-isovaleryl-pyrimidine were prepared by a process in accordance with the following reaction scheme I. ##STR2##
The title compound was prepared in accordance with the method described in Org. Synth. Coll. vol. 2, 422 (1969), starting from ethyl-acetoacetate and urea.
45 g (0.36 M) of 2,4-dihydroxy-6-methyl-pyrimidine have been treated with phosphorous oxychloride in the presence of diethylaniline. After having been refluxed during 3 hours the reaction mixture was cooled and the excess of phosphorous oxychloride was decomposed over ice, then the mixture was neutralized with NaOH, saturated with a NaCl solution and extracted with ether. By separation and evaporation of the ethereal extracts there was obtained a residue which was distilled to yield 57 g of the title compound at B.p. 99.degree./11 Torr.
The product obtained according to paragraph b. above was dissolved in 500 ml of diethylether containing an equivalent amount of triethylamine and 5 g of palladium over charcoal (5%) and the solution was stirred during 51/2 hrs in an atmosphere of hydrogen. After filtration, evaporation and distillation there was obtained the title compound in a yield of about 80%. B.p. 35.degree./12 Torr.
4-Methyl-pyrimidine (0.1 M) was added to 100 ml of ethanol containing 3.5 g (0.1 M) of HCl. While keeping the reaction mixture at 5.degree. there was added over 60 minutes a solution of 9 g (0.12 M) of ethyl nitrite in 60 ml of ethyl alcohol, whereupon the whole was kept under stirring for 1 hour at room temperature. The thus formed 4-formyl-pyrimidine-oxime hydrochloride was separated by filtration, dissolved in water and the aqueous solution neutralized by adding Na.sub.2 CO.sub.3. The title compound was finally obtained by filtration and drying. M.p. 154.degree.-155.degree.. Yield 71%.
A solution of 0.01 M of the oxime prepared according to paragraph d. above, 0.012 M of triphenylphosphine, 0.01 M of carbon tetrachloride and 0.01 M of triethylamine in 50 ml of 1,2-dichloroethane was heated for 2 hours at 60.degree.. The volatile components were taken off and the residue was extracted with 4 fractions of 100 ml of petrolether (B.p. 30.degree.-50.degree.). After evaporation and distillation of the organic extracts 4-cyano-pyrimidine was obtained in a 61% yield.
A solution of 0.05 M of methyl bromide in 15 ml of ether was added to 0.04 at.gr. of magnesium turnings in 15 ml of dry ether and the suspension obtained was refluxed until complete solution of the magnesium present (30 min). The solution was then cooled to -15.degree. and a solution of 0.025 M of 4-cyano-pyrimidine in 20 ml of ether was added thereto. 50 ml of ether was further added to the reaction mixture and stirring was carried out for 30 min. at -10.degree., then for 30 min. at room temperature.
The mixture was then poured onto 100 g of ice, acidified with conc. H.sub.2 SO.sub.4 and stirred 15 min. at room temperature. After neutralisation with solid sodium carbonate, continuous extraction with ether and evaporation of the ethereal extracts there was obtained a residue which was purified by preparative gas chromatography by using a CARBOWAX column 20M. 4-Acetyl-pyrimidine was obtained in 53% yield.
MS:m/e (%):
By replacing in the hereinabove given procedure methyl bromide by ethyl bromide, the title compound was obtained in 11% yield.
MS:m/e (%)__________________________________________________________________________0 1 2 3 4 5 6 7 8 9__________________________________________________________________________20 -- -- -- -- -- -- 13.7 27.7 36.3 97.530 1.4 -- -- -- -- -- -- 1.1 1.2 3.240 .8 1.6 1.4 1.8 -- -- -- -- -- --50 1.2 11.0 73.2 43.9 2.7 4.0 9.8 100. 2.6 --60 -- -- -- -- -- -- -- -- -- 1.270 -- -- -- -- -- -- -- -- -- 51.280 97.8 26.5 1.8 -- -- -- -- -- -- --90 -- -- -- 1.8 19.6 1.5 -- -- -- --100 -- -- -- -- -- -- 1.6 27.8 75.2 4.7110 -- -- -- -- -- -- -- -- -- --120 -- 1.6 -- -- -- -- -- -- -- --130 -- -- -- -- -- 13.5 41.0 3.4__________________________________________________________________________
By replacing in the above given procedure f. methyl bromide by isobutyl bromide, the title compound was obtained in 18% yield.
MS:m/e (%)__________________________________________________________________________0 1 2 3 4 5 6 7 8 9__________________________________________________________________________20 -- -- -- -- -- -- 4.1 16.3 -- 21.530 -- -- -- -- -- -- -- -- 1.3 15.740 2.5 89.9 6.0 18.5 -- -- -- -- -- --50 -- 4.5 28.6 21.2 2.4 5.8 3.4 52.3 2.4 --60 -- -- -- -- -- 1.5 1.5 3.9 1.3 13.170 1.1 1.5 -- -- -- -- -- 2.5 1.5 32.380 100. 17.6 2.3 2.6 1.2 14.4 1.3 -- -- --90 -- 3.6 1.6 3.1 16.1 2.5 -- -- -- --100 -- -- -- -- -- 1.9 1.5 19.5 41.8 4.7110 1.9 -- -- -- -- -- -- -- -- 1.6120 1.1 11.3 7.4 3.4 -- -- -- -- -- --130 -- -- -- 2.7 2.0 2.6 4.7 2.1 -- --140 -- -- -- -- -- -- -- -- -- 18.3150 2.4 -- -- -- -- -- -- -- -- --160 -- -- -- -- 17.5 2.5__________________________________________________________________________
2-Methyl-4-acetyl-pyrimidine, 2-methyl-4-propionyl-pyrimidine and 2-methyl-4-isovaleryl-pyrimidine were prepared by a process in accordance with the following reaction scheme II. ##STR3##
A solution of 405 g (2.5 M) of ethyl ortho-acetate and 295 g (2.5 M) of ethyl acetoacetate in 500 ml of methylalcohol was refluxed for 15 min. During reflux a constant flow of gaseous ammonia was bubbled through the solution. After evaporation of the solvent, the formed pyrimidine was precipitated by adding 500 ml of ether. 190 g of the title compound was thus obtained (yield 61.3%). The further steps to convert the obtained 4-hydroxy-2,6-dimethyl-pyrimidine into the desired acyl pyrimidine were carried out in accordance with the procedure described in steps b. to f. given above.
MS:m/e (%): 27 (3.1), 29 (3.6), 38 (2.6), 39 (5.1), 40 (5.1), 41 (6.7), 42 (82.0), 43 (78.5), 51 (3.1), 52 (19.5), 53 (30.8), 66 (20.5), 67 (15.9), 93 (72.3), 94 (100), 95 (6.1), 108 (33.3), 136 (95.9), 137 (7.2).
NMR: 2.69 and 2.80 (6H, 2s), 7.65 and 8.85 (2H, d, J= 5 cps) .delta. ppm;
IR: 3050, 3020, 2980, 2940, 1715, 1570, 1435, 1395, 1363, 1300, 1272, 1170, 1125, 1097, 1050, 996, 980, 960 and 852 cm.sup.-1.
MS:m/e (%):__________________________________________________________________________0 1 2 3 4 5 6 7 8 9__________________________________________________________________________20 -- -- -- -- -- -- 5.9 18.6 -- 54.830 -- -- -- -- -- -- -- 1.5 2.7 7.340 4.7 10.0 72.7 3.7 -- -- -- -- -- --50 -- 3.8 21.6 25.0 2.9 2.8 6.7 56.2 2.1 --60 -- -- -- -- 1.7 2.8 18.2 7.2 2.1 3.870 -- -- -- -- -- -- -- -- 1.7 2.480 2.9 2.7 1.8 -- -- -- -- -- -- --90 -- 1.3 1.5 62.1 100. 20.8 2.2 -- -- --100 -- -- -- -- -- -- -- 1.8 13.5 3.3110 -- -- -- -- -- -- -- -- -- --120 2.2 24.1 63.3 5.6 -- -- -- -- -- --130 -- -- -- 1.7 -- -- -- -- -- --140 -- -- -- -- -- -- ------ -- 9.4150 36.5 2.9__________________________________________________________________________
MS:m/e (%):______________________________________0 1 2 3 4 5 6 7 8 9______________________________________20 -- -- -- -- -- -- -- 4.4 -- 7.530 -- -- -- -- -- -- -- -- -- 5.640 1.4 17.2 32.2 6.3 6.7 -- -- -- -- --50 -- -- 6.1 8.2 -- -- -- 26.5 -- --60 -- -- -- -- -- 1.5 4.5 2.6 -- 3.770 -- -- -- -- -- -- -- -- -- --80 -- -- -- -- -- 1.9 -- -- -- --90 -- -- -- 30.0 100. 10.3 -- -- -- --100 -- -- -- -- -- -- -- -- 13.1 1.9110 -- -- -- -- -- -- -- -- -- --120 -- 2.6 15.8 1.9 -- -- -- -- -- --130 -- -- -- -- -- 4.7 3.8 2.3 -- --140 -- -- -- -- -- -- -- -- -- 1.4150 2.3 -- -- -- -- -- -- -- -- --160 -- -- -- 16.5 2.7 -- -- -- -- --170 -- -- -- -- -- -- -- -- 10.9 2.9180______________________________________
2-Methyl-4-acetyl-pyrimidine can also be prepared in accordance with the procedure illustrated by the following reaction scheme. ##STR4##
US Referenced Citations (3)
| Number |
Name |
Date |
Kind |
|
3764601 |
Evers et al. |
Oct 1973 |
|
|
3843804 |
Evers et al. |
Oct 1974 |
|
|
3857972 |
Evers et al. |
Dec 1974 |
|
Patent Grant
4166869
