DE2141916B2 - 2-METHYL-5,7-DIHYDROTHIENO SQUARE BRACKET ON 3,4 SQUARE BRACKET FOR PYRIMIDINE, METHOD FOR ITS MANUFACTURING AND USE - Google Patents

Description

The prior art includes various substituted pyrimidines, such as that from US Pat 29 69 361 known 4-chloro-6,7-dihydro-2-methyl-5H-cyclopenta [d] pyrimidine, which is said to be smells of roasted corn; any taste or flavor enhancing effects or organoleptic effects However, properties are neither given nor assumed for this compound.

In DT-AS 11 14 497 pyrimidines, including cyclopentapyrimidines, which are substituted in the 4- and 5-positions called that proposed as intermediates for pharmaceuticals and for chemical synthesis will. For any taste or flavor enhancing effects or organoleptic Properties of these compounds are not pointed out.

In Chemical Abstracts, 52 (1958) 7323e, 4-methyl-5,6-tetramethylene pyrimidine is mentioned, without however, some use is indicated for this compound. In J. Am. Chem. Soc, 81 (1959), Pages 3108-3114 is a synthesis of the 6,7-dihydro-5H-cyclopenta [d] pyrimidine described. In the published Dutch application 68/1299 it is stated that that the 2- and S-methyl-SH-öJ-dihydrocyclopenta [b] pyrazine have a chocolate or peanut flavor. The US-PS 32 72 811 shows a variety of pyrimidines, but no taste or flavor enhancing effect or organoleptic Characteristic.

The invention relates to 2-methyl-5,7-dihydrothieno [3,4-d] pyrimidine the formula

60

This product is a colorless crystalline material that melts at 64.5 to 65 ° C and is vigorous after roasting fresh, sweet nuts smells with a certain roasted maize character.

The new pyrimidine can in the usual way by reducing dehalogenation of the corresponding

4-chloropyrimidines can be obtained with zinc dust. the Reduction with zinc dust is preferably carried out in a carrier medium, in particular a lower alkanol, such as ethanol and in the presence of an acidic agent such as ammonium chloride. The reaction becomes preferable at this time carried out so that a reaction time of 1 to 2 hours is required, with about 1.5 hours to be favoured.

The end product produced can of course be neutralized and washed for isolation and purification and be dried. The bicyclic pyrimidine can be purer by conventional purification methods or in substantially pure form. The product can be produced by distillation, extraction, Crystallization or preparative chromatography can be purified and / or isolated.

It is particularly noteworthy that the pyrimidine described here can be used to change, vary, Enhancement, modification, enhancement or otherwise enhancement of the taste of a broad Variety of products can be used that can be ingested, consumed or otherwise organoleptically be perceived. The term change should be understood in its broadest form be, d. That is, that an otherwise flabby, relatively tasteless substance has a certain taste or a A flavor note is given or supplemented, or that an already existing flavor character is increased or rinded where the natural taste is deficient in any respect or that an existing taste impression to modify the organoleptic character is supplemented.

The pyrimidine mentioned can therefore be used for spices or spice mixtures. Such mixtures can by adding or enhancing a natural or artificial taste to the overall taste character contribute or provide practically the entire taste and / or aroma character of a consumable product. Particularly The pyrimidine according to the invention is useful for the contribution of sweetish and nut-like taste notes to artificial essential oils, peppermint oil and spearmint oil. It is also suitable for rounding off and improving the flavor character of nut, bread and vanilla flavor mixes. The term food or food, as used in the context of the present description, includes both solid and also liquid products that can be consumed by humans and animals, which are usually - but not necessarily - have some nutritional value. Such foods or dishes include meat, sauces, Soups, foodstuffs or casual foods, malt and other alcoholic or non-alcoholic beverages, Milk and dairy products, nut butters such as peanut butter and other spreads, foods from the sea, such as fish, crustaceans or molluscs, confectionery, breakfast side dishes, baked goods, Vegetables, nutrients, low-alcohol beverages, snacks, dog and cat food, and other veterinary products.

In the context of the present description, the term tobacco is intended to mean natural products, such as Burley, Turkish or Maryland tobacco or heat treated tobacco including of tobacco-like or basic tobacco products, such as reconstituted or homogenized leaves,

as well as tobacco substitutes intended to replace natural tobacco, such as lettuce and cabbage leaves. To tobacco and tobacco products include the products intended for smoking such as cigarettes, cigars, pipe tobacco and also products like snuff or chewing tobacco.

The term "consumable" or ingestible material is intended to mean either food or meal as well as tobacco products.

The pyrimidine can be combined with one or more carriers or vehicles for its addition certain products. Carriers can be edible or other suitable materials such as ethyl alcohol, propylene glycol, or water. Carriers include gum arabic, karra'geen, other gums or mucilages. The pyrimidine can be prepared by conventional means such as spray drying or Drum drying can be mixed with the carriers. Such carriers can also contain materials for the Include coacervation of the pyrimidine (as well as other condiments) to provide encapsulated products.

If the carrier is formed by an emulsion, the seasoning mixture can also contain emulsifiers, such as mono- and diglycerides of fatty acids. With these carriers or carrier means, the desired physical form of the mixture can be obtained.

It should be clear to those skilled in the art that the pyrimidine can be used in any suitable product to be flavored Time of manufacture of the end product can be added. So can the pyrimidine if there is to change or otherwise modify the taste of a food, which is intended for any Cooking or heating process determined the original mixture, the dough, the emulsion or can be added to the batter. Alternatively, it may if the losses are due to volatilization during a previous preparation would be too high, also added in a later phase of the food preparation will.

If the product is used for the treatment of tobacco products, the additive can, for example, through Spraying, dipping, or other known means. The pyrimidine can added during storage or final spray treatment of the tobacco or to any earlier stage of treatment or preparation of the tobacco can be applied.

The applied amounts of the pyrimidine should be sufficient to give the treated product the desired To give flavor character; on the other hand, however, the application is excessive The amount of pyrimidine is not only superfluous and uneconomical, but in some cases it can also be too large Amount to an imbalance of taste or other organoleptic properties of the for lead to the consumption of a certain product.

The appropriate amount to use will depend on the final food, tobacco product, or other consumable product; as well as the extent and type of taste originally present in the product; the further processing or treatment to which the product will be subjected; of regional or other preference factors; the type of storage of the product, if such is provided, and the treatment or preparation, such as baking or roasting, which are carried out by the end user before consumption. The terms effective amount and sufficient amount are accordingly to be understood in connection with the present invention as being quantitatively appropriate for changing the taste of food, tobacco and other ingestible products.
Accordingly, it is preferred that the final composition contains from about 10 ~ ⁹ ppm to about 200 ppm pyrimidine. In particular, from about 0.0001 to about 200 ppm is used in food mixes for flavor enhancement

ίο desired and preferred are from about 0.01 to On the other hand, about 20 ppm pyrimidine can be used in the end product for positive flavors Tobacco compositions, depending on whether cigarette tobacco, pipe tobacco, cigar tobacco, chewing tobacco or Snuff is manufactured to contain from about 0.01 ppm to about 100 ppm pyrimidine. The applicable Amount of pyrimidine depends on many factors, the desired taste, other available Components or final use.

The pyrimidine according to the invention can be used individually or in the form of mixtures as a fragrance. It can can be used to impart a nut-like fragrance. The fragrance according to the invention can be used as a fragrance Thienopyrimidine formulated into a "perfume composition" or be used as a component of such a perfume composition.

A perfume composition generally includes a small? About an effective amount of pyrimidine according to Invention and perfume auxiliaries and additives, such as alcohols, aldehydes, ketones, nitriles, Esters and often hydrocarbons, which are mixed in, so that the combined fragrance effects of the individual components produce a pleasant or desired fragrance.

Such perfume compositions usually contain:

(a) Connections which determine the main note or the "bouquet" of the composition;

(b) modifications that round off and accompany this main note;

(c) Fixatives, which include fragrant substances that move the perfume through all stages of evaporation give a special touch and substances that delay evaporation and

(d) "Scent tips", which are usually formed by low-boiling, fresh-smelling products.

In perfume compositions, the individual components contribute their own particular fragrance character; the overall effect of the perfume compositions then results from the superimposition of the individual effects of the components. Thus, the compound according to the invention can be used to change the aroma characteristics of a perfume composition, for example by increasing or refining or modifying the fragrance effect of other components of the composition.
The amount of the compound according to the invention which is found to be effective in the perfume composition depends on many factors, such as the other constituents, their amounts and the desired effects. It has been found that perfume compositions with small amounts, such as about 2% of the compound of the invention or even less, can be used to impart a pleasant fragrance to soaps, cosmetic articles and other products. The amount applied

can reach up to 50% or more and is determined taking into account the cost, type of End product, the expected effect and the specially desired fragrance

The thienopyrimidine according to the invention can be used alone or in a perfume composition as a fragrance component found in washing powders, cleaning agents and soaps as well as in room air fresheners and Deodorants, in perfume, eau de cologne, fau de toilette, bath preparations such as bath oil and bath salts, hair preparations ι ο advise, such as varnishes, brillantines, pomades and shampoos, cosmetic preparations such as creams, deodorants, Hand lotions and sunscreens; in powders such as talc, powder powder, or face powder. at Small amounts, such as about 0.01% des can be used as a fragrance component of a perfumed product Pyrimidines are sufficient to produce a nut-like or seed-like odor. Generally no more than 0.3% are required

In addition, the perfume composition or fragrance-substance mixture can be a carrier or a carrier for contain the pyrimidine alone or with other ingredients. The carrier means can be a liquid such as Alcohol, glyco! or the like. The carrier can be an absorbing or adsorbing solid, such as a rubber or slimy substance or through components for Encapsulation of the mixture will be formed.

The examples illustrate the invention.

All parts, proportions, proportions and percentages given in this description are unless otherwise stated, based on weight.

example

Preparation of 2-methyl-5,7-dihydrothieno [3,4-d] pyrimidine

A mixture of 55.8 g of 2-methyl-4-chloro-5,7-dihydrothieno [3,4-d] pyrimidine, 78.5 g zinc dust, 8.04 g ammonium chloride and 840 ml 67% ethanol is 2 Heated under reflux for hours. After cooling, the insoluble material is removed by filtration.

The solid residue is washed three times with 300 ml of 95% ethanol and the combined The filtrate was concentrated to a volume of about 300 ml. After adding 100 ml of water, the solution becomes extracted three times with 250 ml portions of mathylene chloride. After drying, the solvent is removed in vacuo and crude 2-methyl-5,7-dihydrothieno [3,4-d] pyrimidine is obtained.

Chromatography on 820 g of silica and elution with 1% methanol in methylene chloride as well Recrystallization from hexane mixed with decolorizing activated charcoal gives 17 g of pure 2-methyl-5,7-dihydrothieno [3,4-d] pyrimidine as short pale white needles that melt at 64.5 to 65 ° C.

The scent of this pyrimidine in 0.1% alcoholic solution on a strip of blotting paper is a sharp smell of freshly roasted sweet nuts with a roasted maize character. At this concentration, the scent seems to disappear due to anosmia. In an aqueous solution with 0.001 ppm, the Prodi: kt has a sweet, roasted nut and roasted maize character with a slightly astringent tendency. At 0.003 ppm in water, it tastes like roasted corn and roasted peanuts with an astringency effect similar to peanut skin. At 10- ^e ppm in chicken broth, it enhances the root vegetable flavor notes.

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40

55

60 further that the compound in very low concentrations in the range of 10 ~ ^ä ppm begins to enhance the sweet taste of food has been found. At concentrations of ΙΟ "ppm imparts ³ aqueous solutions of a sweet pleasant, non bitter aftertaste It can thus be used as a reinforcing substance for reducing the required amount of artificial sweeteners or it helps ^d: e. Amount of natural sweeteners, such as sugar, to Reduce.

Application example t

A cheddar cheese seasoning mix was made by mixing the following ingredients together into the specified quantities produced:

component lot (Parts) Methyl hexyl ketone 1.5 Diacetyl 14.2 Isovaleric acid 40.8 Hexanoic acid 158.9 Butyric acid 244.8 Caprylic acid 534.8 Thienopyrimidine according to Example 1 5.0

45 The above cheese seasoning is introduced into mild cream cheese spread and tried on crackers: The cheese spread had a good, sharp cheddar taste.

Application example 2

A nut-like mass is made using conventional methods by mixing cottonseed oil, Wheat germ, cane sugar and glycerin made into a smooth pulp and then topped with fresh white egg offset. A seasoning mixture containing the thienopyrimidine is then added to the dispersion Example 1 contains.

The resulting nut-like edible product has the taste and appearance of freshly roasted ones Akaju nuts.

Application example 2

link Parts Maltol 3.0 Acetaldehyde (50% in ethanol) 20.0 isobutyraldehyde 16.0 Isovaleraldehyde 42.5 Benzyl alcohol 10.0 Methyl sulfide 0.4 Methyl disulfide 0.4 Isobutyl acetate 0.1 Isoamyl acetate 0.2 Phenylethyl acetate 0.6 Diacetyl (10% in ethyl alcohol) 0.3 Acetophenone 1.0 Furfural (10% in ethyl alcohol) 1.0 Benzaldehyde 1.0 Isoamyl alcohol 0.5 Phenylethyl alcohol 3.0

100.0

A product with a chocolate-like taste note is made by mixing the following ingredients together manufactured:

link

Share connection

Parts

2-methyl-5,7-dihydrothieno [3,4-d] pyrimidine
2,3,5,6-tetramethylpyrazine

65 35

One part by weight of this product is mixed intensively with 99 parts of cocoa flavor base. The resulting mixture is then mixed with propylene glycol such that a 10% propylene glycol solution is obtained. This is then added in an amount of 0.2% to a ready-made or instant beverage powder with chocolate flavor, whereby a characteristic sweet milk chocolate flavor is obtained.

Application example 4

A perfume component was produced by mixing the following ingredients together:

"5

component

Quantity (parts)

Geranium, bourbon

Patchouli

Vetivert (grass oil)

Cinnamon (cassia)

Thienopyrimidine according to Example 1 Lavender

Orris resin

Methyl ionone

Coumarin

Musk, xylene

Terpineol

450 40 10

100 30 40

100 60 40 20 30

100

The above mixture is a fragrance composition of the "transparent type". The thienopyrimidine will used as a substitute for 20 parts of caraway essence, preserving the natural caraway note of the original perfume remain

Application example 5

A bread spice is made by mixing the following ingredients:

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Lactic acid

acetic acid

Butyric acid

Propionic acid

Pyruvic acid

Ethyl pyruvate

Isovaleraldehyde

(10% in propylene glycol)

Furfural

Benzaldehyde

(10% in propylene glycol)

2-methyl-5,7-dihydro

thieno [3,4-d] pyrimidine

50 20 2 5 3 2

2 12

2 TÖÖ

The above seasoning is made (in an amount of 0.02%) into a prepared bread dough with flour, Tartaric acid and sodium bicarbonate were added.

After baking, the resulting bread has one

excellent "home-baked" corn bread taste and corresponding aroma characteristics as a result

the addition of the 2-methyl-5,7-dihydrothieno [3,4-d] pyr-

imidins.

Application example 5

A vanilla spice is made by mixing the following ingredients together:

link

Parts

Maltol 2

Vanillin 12

Ethyl vanillin 3 Anisaldehyde (1% in propylene glycol) 1 Propylene glycol 70

Ethanol (95%) 12 2-methyl-5,7-dihydrothieno [3,4-d] pyrimidine

(0.1% in propylene glycol) 0.2

100.2

The addition of 2-methyl-5,7-dihydrothieno [3,4-d] pyrimidine brings a distinct "natural" quality of the taste, more than without this connection.

«09550/466

W.

Claims (3)

Patent claims: 1,2-Methyl-5,7-dihydrothieno [3,4-d] pyrimidine, der formula 2. Method of making the connection according to claim 1, characterized in that the 4-chloropyridine derivative is known per se Way dehalogenated with zinc dust in the presence of an acidic substance. 3. Use of the pyrimidine compound according to claim 1 for seasoning and flavoring and for seasoning and fragrance compositions.