DE2141916A1 - Bicyclic pyrimidine derivatives, their preparation and use - Google Patents

Description

026-17 WP 20.8.1971

INTERNATIONAL FLAVORS & FRAGRANCES INC., New York (V.St.A.)

Bicyclic pyrimidine derivatives, their Manufacture and use

The invention relates to bioyclic pyrimidine derivatives the general formula

in which X is S, 0 'or CHp and R _{1 is} a hydrogen or halogen atom or an alkyl, alkoxy, alkylthio or cycloalkylthio radical, Rp is a hydrogen atom or an alkyl or alkylthio radical and R ₁₅ , R ^, R ₁ - and Rg, which can be identical or different, denote hydrogen atoms or alkyl radicals, in particular lower alkyl radicals having 1 to 5 carbon atoms, where R. and Rp are not both intended to represent alkylthio radicals at the same time.

026- (IFF 2162/2176/2177) -NÖE (8)

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The pyrimidine derivatives according to the invention are distinguished characterized by special taste and fragrance effects and the invention therefore includes their use for seasoning and flavoring as well as for spices and fragrance compositions.

The prior art includes various substituted pyrimidines, such as that known from US Pat. No. 2,969,361 4-chloro-6,7-dihydro-2-methyl-5H-cyclopenta- [dj-pyrimidine, which is said to smell of roasted corn; any taste or flavor enhancing effects however, organoleptic properties are required for this Connection neither specified nor suspected of her.

In DT-AS 1114 497, substituted in the 4- and 5-positions Pyrimidines including Cyelopentapyrimidines called as intermediates for medicines and for chemical synthesis can be proposed. Any taste or flavor enhancing effects or Organoleptic properties of these compounds are not pointed out, nor are any of the new cyelopentapyrimidines of the present invention mentioned in this DT-AS shown.

In Chemical Abstracts, j52 (1958) 7323e, 4-methyl-5,6-tetramethylene pyrimidine but without suggesting any use for this compound will. In the J.Am.Chem.Soc. 8l (1959), pages 5108-3114 a synthesis for the 6,7-dihydro-5H-cyclopenta- (jTJ-pyriniidin described. In the published Dutch application 68/1299 it is stated that the 2- and 5-methyl-5H-6,7-dihydrocyclopenta- (b) -pyrazirie have a chocolate or peanut flavor. The US PSi. 5,272 8II shows a variety of pyrimidines, but no taste or taste

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enhancing effect or organoleptic property.

It has now been found that the above-mentioned cyclopentapyrimidines are capable of a variety of foods or the consumption or intake by humans or animals To give products a wide variety of flavor effects. Accordingly, the present invention aims to change the taste with such "consumable" products Addition of a small but effective amount of at least one of the above-mentioned pyrimidine derivatives.

The following are the bicyclic according to the invention Pyrimidine derivatives include thienopyrimidines, cyclopentapyrimidines, and oxacyclic pyrimidines more im individually described.

Useful thienopyrimidines include compounds of the formula

in which R ^, R ₂ , R ,, R ^, R, - and Rg are identical or different and denote hydrogen atoms or alkyl groups.

With these sulfur-containing pyrimidines according to the invention is a dihydro-

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thiophene ring anelllert. The five-membered ring containing sulfur can have one or more alkyl groups as substituents and the pyrimidine ring can likewise be substituted with one or two alkyl groups. The substituents on the sulfur-containing five-membered ring can in some cases be in the geminal position. In practicing the invention, it is generally preferred that the substituent or substituents be formed by lower alkyl groups, especially alkyl groups having 1 to 6 carbon atoms and P preferably 1 to Z> carbon atoms.

A specific example of the sulfur-containing pyrimidines prepared according to the invention is 2-methyl-5,7-dihydrothleno- £ j5 * 4-d] -pyrimidine the formula:

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

The new pyrimidines prepared according to the invention can by reducing dehalogenation of the corresponding 4-chloropyrimidines with zinc dust or by catalytic Hydrogenation can be obtained. The reduction with zinc dust is preferably carried out in a carrier medium, in particular one lower alkanol such as ethanol and in the presence of an acidic agent such as ammonium chloride. The reaction is

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preferably carried out so that a reaction time of 1 to 2 Hours is required, with about 1.5 hours being preferred.

If dehalogenation is carried out by catalytic hydrogenation, can also be used within an inert carrier medium. For example, alkanols, especially lower alcohols, how ethanol and methanol are used. Suitable catalysts include palladium and bearium carbonate.

Of course, according to the invention, intermediate products and finished products can be used for isolation and purification the desired substance can be neutralized, washed and dried. The bicyclic pyrimidines can after conventional purification processes can be obtained in purer or substantially pure form. So can the products purified and / or isolated by distillation, extraction, crystallization, preparative chromatography and the like will.

Suitable cyclopentapyrimidines include compounds of the formula

H ^R 5

in the R. an alkyl, alkoxy, alkylthio or cycloalkylthio radical or a hydrogen atom, R _{2 is} a hydrogen atom

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or an alkyl or alkylthio radical and R ,, R ^ ,, R ₁ - and Rg, which can be identical or different, denote hydrogen atoms or lower alkyl radicals having 1 to 5 carbon atoms, where R ₁ and R _{2 are} not both intended to represent alkylthio radicals at the same time .

Of these compounds, new are those in which R _{2 is} not hydrogen. In practicing the invention, it is generally preferred that the alkyl groups and alkoxy groups have especially 1 to 4 carbon atoms, the alkylthio groups especially 1 to 3 carbon atoms, and the cycloalkylthio groups especially 3 to 5 carbon atoms. In general, the cyclopentapyrimidines according to the invention are pyrimidines with a 5-membered hydrocarbon ring fused on the d-side.

A cyclopentapyrimidine according to the invention is 6,7-dihydro-5H-2-methyl-cyclopenta- £ dI-pyrimidine the formula

This compound is a white crystalline solid with notes of nut flavors, like sweet crackers with a toasted flavor Roasted maize character reminiscent of nuts.

Another compound according to the invention is 4-methoxy-6,7-dihydro-5H-2-methyl-cyclopenta-Cd] pyrimidine the formula

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OCIL

This product has a boiling point of 65 to 64 C. 0.25 irariHg and a nutty taste.

Yet another compound according to the invention is the 4-ethoxy-6, T-dihydro-SH - ^ - methyl-cyclopenta- £ d] -pyrimidine the formula

OCH ₂ CH ₅

This product is a very pale yellow liquid with a boiling point of 63 to 64 ° C at 0.25 mmHg. It owns nutty flavor character and can be used in condiments for baked goods.

Another product according to the invention is that

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the formula

CH

N.

OCH ₂ CH ₂ CH ₅

This product is a colorless liquid with a boiling point of 8l to 83 ° C at 0.15 mmHg and tastes good sweet roasted nuts.

Another material according to the invention is the 4-isobutoxy-6,7-dihydro-5H-2-methyl-cyclopenta - [; <il- ^{pyrinildin of} the formula ■

CH

■■ *,

CH,

OCH ₂ -CH
CH

This product is a colorless liquid with a boiling point of 77 ⁰ C at 0.15 mmHg and has fruity, nut-like flavors with a slight butter-like aftertaste *

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Another material according to the invention is the 2-methylthio-6,7-dihydro-5H-cyclopenta-fcQ-pyrimidine der
formula

This product is a yellow pest with a fried onion flavor.

Yet another material according to the invention is the ^ -n-propylthio-öjT
midin the formula

This product is a yellow liquid with a boiling point of 99 to 101 ⁰ C.

Another example of the compounds according to the invention is the ^ methylthio-öjT
ta-fcQ-pyrimidine of the formula

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CH

NS,

This product is a light yellow pest with a nutty green vegetable aroma and taste.

Yet another material which exemplifies the invention is 4-cyclopentylthio-6,7-dihydro-5H-2-methyl-oyclopenta-jjl3-pyrimidine the formula

This product is a very light amber yellow liquid with a boiling point of 116 to 118 ° C at 0.15 mmHg and has a sweet onion flavor.

The new cyclopentapyrimidines according to the invention can be obtained in various ways:

The 6, T-dihydro-SH ^ -alkyl-oyclopenta- [ja] -pyrimidines,

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such as the 6,7-dihydro-5H-2-methyl = cyclopenta - [\ ri - pyrimidine can by reducing dehalogenation of the corresponding ^ halo-öjT-dlhydro-SH ^ -alkylcyelopenta-Qi] -pyrimidines can be obtained. This reaction takes place under pressure in an aqueous solution in the presence of a suitable solvent, e.g. ethers such as diethyl ether, aromatic hydrocarbons such as benzene, toluene and the like. Useful halogen derivatives are the chlorine, bromine and iodine compounds. The presence of a catalyst is desirable and appropriate Catalysts include palladium, platinum and Raney nickel and the catalyst is preferably supported on such as Applied coal. The pressure applied is generally below 10 at. The reaction is considered complete when the theoretical amount of hydrogen is consumed.

The ^ -alkoxy-6,7-dihydro-5H-2-alkyl-cyclopenta-Cdlpyrimidines, such as 4-methoxy-6,7-dihydro-5H-2-methylcyclopenta-fjfj-pyrimidine can be obtained by etherification of the corresponding 4-halo-6,7-dihydro ~ 5H-2-alkyl-cyelopenta- [d ~ lpyrimidines can be obtained. Suitable halogen compounds are the chlorine, bromine and iodine compounds. The reaction takes place with formation of an alkali metal alkoxide and reaction of the alkoxide with the 4-halo-6,7-dihydro-5H ~ 2-alkyl-cyclopenta- (jd] I-pyrimidine under reflux, as a result of which the halogen substituent is displaced by the alkoxy substituent will.

The ^

pyrimidines, such as the ^ -
methyl-cyclopenta-Qi ^ -pyrimidine and the 4-cycloalkylthio-6, 7-dihydro-5H-2-alkyl-cyclopenta- [d '] - pyrimidines, such as the ^ -Cyclopentylthio-ö, 7-dihydro-5H- 2-methyl-cyclopenta-QfJ-pyrimidine can by reacting the appropriate

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4-halo-6,7-dihydro-5H-2-alkyl-cyclopenta- |] d] pyrimidines with a suitable alkyl mercaptan or cycloalkyl mereaptan in a suitable solvent. Useful Halogen compounds are the chlorine, bromine and iodine compounds. The reaction is preferably carried out in a solvent, such as ethanol, methanol and isopropanol and under reflux conditions.

The 2-alkylthio-6,7-dihydro-5H-cyclopenta- £ d] -pyrimidines, such as 2-methylthio-6,7-dihydro-5H-cyclopenta - [] crj-pyrimidine can be obtained by reducing dehalogenation of the corresponding 4-halo-6,7-dihydro-5H-cyclopenta- (jä '] - pyrimidines will. This reaction takes place under reflux conditions in the presence of zinc dust and ammonium chloride.

The cyclopentapyrimidines according to the invention are prepared as described from the corresponding 4-halo-6,7-dihydro-5H-cyclopenta-jjd] pyrimidines. If Cyclopentapyrimidine are desired, the fused five-membered ring is mono- or polyalkylsubstituiert, these can be mono- or polyalkyl-substituted by reaction with 2-Carbäthoxycyclopentanons acetamidine at temperatures of about 40 to 50 ⁰ C while stirring well be made of a. Substituted cyclopentanone carboxylic acids are known, such as, for example, 3-methylcyclopentanone (2) carboxylic acid (see Beilstein, A II, No. 10, p. 422), 1,3-dimethylcyclopentanone (2) carboxylic acid (see Beilstein , A II, No. 10, p. 424) and 3-methyl-1-propylcyclopentanone- (5) -carboxylic acid (see Beilstein, A II, No. 10, p. 4JO). Reaction with acetamidine yields hydroxycyclopentapyrimidine which is then converted to the corresponding halocyclopentapyramidine by methods such as those described in US Pat. No. 2,961,561. The halocyclopentapyrimidine is then, as already shown, dehalogenated in a reducing manner.

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Obviously, the intermediate and final products obtained will be neutralized, washed and dried to achieve the desired substances. The new Cyelopentapyrimidines can can be obtained in purer or substantially pure form by conventional purification processes. So can the products purified and / or isolated by distillation, extraction, crystallization, preparative chromatography and the like will.

Suitable oxacyclic pyrimidines according to the formula

in R. an alkyl radical or a halogen or hydrogen atom and Rp, R _{1 , R 2} , R 1 - and R>, which can be identical or different, denote hydrogen atoms or alkyl radicals.

Considered more in detail, the oxacyclic pyrimidines according to the invention are compounds with at the d-side of the pyrimidine fused tetrahydrofuran ring. The oxygen-containing ring can be substituted with one or more alkyl groups, as can the pyrimidine ring may have one or two alkyl groups or a halogen atom as a substituent. The substituents of the oxygen-containing Ringes can in some cases be in a geminal position

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are present. In practicing the invention, it is preferred that the substituent or substituents formed by lower alkyl groups, in particular alkyl groups having 1 to 6 and preferably 1 to 4 carbon atoms will. Chlorine, bromine or iodine are preferred as halogen substituents.

A special example of the oxacyclic pyrimidines considered here is 2-methyl-5,7-dihydrofuro- [J5i4-d3-pyrimidine the formula

This product is a white pest with something similar to roasted corn Smell and a sweetish roasted rice taste.

Another compound according to the invention is 2,7-dimethyl-5 <7-clihydrofuro-Q5,4-d3-pyrimidine the formula

CH,

This product is a colorless liquid with a roasted corn cracker aroma and taste.

Yet another compound according to the invention is

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the 2,5,7-trimethyl-5,7-dihydrofuro £ 3,4-d3-pyrimidine der formula

This product is a colorless liquid with a sweet nutritional note.

Other new products made according to the invention are 2-methyl-4-chloro-5,7-dihydrofuro- {25,4-d] -pyrimidine, 2,7-dimethyl-4-chloro-5,7-dihydrofuro- [2 , 4-dIl-pyrimidine and 2,5,7-trimethyl-4-chloro-5,7-dihydrofuro-n5,4-d] | -pyrimidine. These new products are all useful intermediates for the preparation of the new oxacyclic pyrimidines of the invention.

The new oxacyclic pyrimidines prepared according to the invention can be obtained by reacting a carbalkoxytetrahydrofuranone with ethamidine hydrochloride in the presence of a suitable base in a suitable solvent with formation of the alkylhydroxy-dlhydrofuropyrimidine. Suitable bases are alkali metal hydroxides and carbonates and alkoxides such as potassium carbonate, sodium ethoxide and sodium hydroxide. Suitable solvents include lower ones Alkenols such as ethanol and the like, water and mixtures thereof. The reaction is preferably carried out at room temperature over a period of about 17 to 97 hours.

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The addition of a halogenating agent to the alkylhydroxydihydrofuropyrimidine under reflux conditions leads to the formation of the corresponding alkylchlorodihydrofuropyrimidine. to suitable halogenating agents include phosphorus oxychloride and the like.

The alkylohlordihydrofuropyrimidine can be converted into the corresponding alkyldihydrofuropyrimidine by reducing dehalogenation being transformed. This reaction is carried out under reflux conditions in the presence of a reducing dehalogenating agent such as ammonium chloride and zinc dust.

Of course, the intermediate and end products according to the invention can be used to obtain and purify the desired Substances are neutralized, washed and dried. The oxacyclic pyrimidines can by conventional Purification processes can be obtained in purer or substantially pure form. The products can be distilled, Extraction, crystallization, preparative chromatography and the like. Purified and / or isolated.

It should be particularly noted that the various pyrimidines and mixtures thereof described herein according to of the invention for changing, varying, enhancing, modifying, enhancing or otherwise improving the taste A wide variety of products can be used, whether ingested, consumed or otherwise be perceived organoleptically. The term change should be understood in its broadest form, i.e. that an otherwise flabby, relatively tasteless substance is given or supplemented with a certain taste or flavor note, or that a existing flavor character increased or

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where the natural taste is rounded off in any Relationship is deficient or that an existing taste impression to modify the organoleptic character is supplemented.

The pyrimidines mentioned can therefore be used for spices or seasoning mixtures. Such mixtures can by Addition or enhancement of a natural or artificial taste to the overall taste character or also contribute deliver practically all of the flavor and / or aroma character of a consumable product. Particularly useful are the different pyrimidines according to the invention for the contribution of sweetish and nut-like taste notes to artificial essential oils, peppermint oil and spearmint oil. They are also suitable for rounding off and improving the flavor character of nuts, bread and Vanilla flavor mixes. The designation food or dish as used in the context of the present description is used, includes. Both solid and liquid, for humans and animals ingestible products, which are usually - but not necessarily - have some nutritional value. Such foods or dishes include meat, Sauces, soups, nutrients or casual foods, malt and other alcoholic or non-alcoholic beverages, Milk and dairy products, nut butters such as peanut butter and other spreads, seafood, such as fish, crustaceans, molluscs and the like, confectionery, breakfast side dishes, baked goods, vegetables, nutrients, low-alcohol Soft drinks, snacks, dog and cat food and other veterinary products and the like.

In the context of the present description, the term tobacco is intended to mean natural products, such as

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wise strong Turkish or Maryland tobacco, heat treated Tobacco and the like, including tobacco-like or base tobacco products such as reconstituted or homogenized leaves and the like, as well as tobacco substitutes intended to replace natural tobacco, such as lettuce and cabbage leaves and the like for tobacco and tobacco products include the products intended for smoking such as cigarettes, cigars, pipe tobacco and also products such as snuff, chewing tobacco and the like.

The term "consumable" or ingestible material is intended to include food or dishes as well Include tobacco products.

If the. Oxacyclic pyrimidines according to the invention are used in seasoning mixtures, they can be used with conventional Flavors or additives are combined. Such co-ingredients or flavor additives are the Those skilled in the art are generally familiar with such uses and are extensively described in the literature. Apart from the requirement that any such auxiliary or additive for the Ingestion permitted and therefore non-toxic and otherwise un-)) must be harmful, conventional materials can be used and in the broadest sense other flavors, carriers, Stabilizers, thickeners, surface active agents, conditioning agents and flavor enhancers are used will.

Common flavoring aids include saturated and unsaturated fatty and amino acids; Alcohols, including primary and secondary alcohols; Ester; Carbonyl compounds such as ketones and aldehydes; Lactones; other cyclic organic materials including benzene derivatives, alicyclics, heterocycles such as furans, Pyridines, pyrazines and the like; sulphurous materials,

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like thiols, sulfides, disulfides and the like? Proteins? Fats or lipids; Carbohydrates? so-called taste potentiators, such as monosodium glutamate, guanylates, and inosinates; natural flavors like cocoa, vanilla and caramel? essential oils and extracts such as anisole, clove oil and the like? artificial flavors such as vanillin and the like.

Stabilizers include preservatives such as sodium chloride and the like, antioxidants such as calcium and calcium Sodium ascorbate, ascorbic acid, butylated hydroxyanisole, butylated hydroxytoluene, propyl gallate and the like, for insertion Serving agents (sequestrants), such as citric acid, Ä'DTA, Pho sphat e etc.

To thickening carrier agents, binders, protective colloids, Suspendierungsraittel, emulsifiers, etc. belong. Such as agar-agar, Karra'geen (Irish chondrus) _s of cellulose and cellulose derivatives such as carboxymethyl cellulose and methyl cellulose, natural and synthetic rubber or gums such as gum arabic, gum tragacanth and the like and other proteinaceous materials, fats, carbohydrates, starches and pectins.

Surface-active agents include emulsifiers such as mono- and / or diglycerides of fatty acids such as capric acid, Caprylic acid, palmitic acid, myristic acid, oleic acid and the like? Lecithin, defoaming and taste dispersing Agents such as sorbitan monostearate, potassium stearate, hydrogenated tallow alcohol and the like *

Conditioning agents include compounds such as Blelch- and ripening agents such as benzoyl peroxide, calcium peroxide, Hydrogen peroxide and the like? Strength modifiers, such as

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Peracetic acid, sodium chloride, sodium hypochlorite, propylene oxide, Succinic anhydride and the like; Buffers and neutralizing agents, "such as sodium acetate, ammonium bicarbonate, Ammonium phosphate, citric acid, lactic acid, vinegar and the like; Dyes such as carminic acid, koschenilla, turmeric yellow, Curcumin, tried and tested food and medicinal colors and the like; Firming agents, such as sodium aluminum sulfate, Calcium chloride and calcium gluconate; Texturizers; Anti-caking agents such as calcium aluminum sulfate and tricalcium phosphate; Enzymes; Yeast foods such as calcium lactate and calcium sulfate; Nutritional additives such as iron salts such as perriphosphates, Perripyrophosphates, perrogluconate, and the like; Riboflavin; Vitamins; Zinc sources such as zinc chloride, zinc sulfate and the like.

The various pyrimidines mentioned above or mixtures containing them can be mixed with one or more Carriers or carriers can be combined for their addition to certain products. Carriers can be edible or otherwise suitable materials such as ethyl alcohol, propylene glycol, water, and the like, supports include materials such as gum arabic, karra'geen, other gums or mucilages, etc. The pyrimidines can be replaced by conventional Means such as spray drying, drum drying and the like can be mixed with the carriers. Such carriers can also Materials for the coacervation of the pyrimidines include (as well as other condiments) to provide encapsulated Products.

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

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Mixture can be obtained.

It should be clear to those skilled in the art that the various pyrimidines lead to any suitable product to be flavored Time of manufacture of the end product can be added. So can the pyrimidines if they to change or otherwise modify the taste of a food, which is suitable for any cooking or Heating process determined the original mixture, the Dough, emulsion, batter or the like can be added. Alternatively, they can if the losses are by volatilization would be too high during a previous preparation, also in a later phase of the food preparation can be added.

If the products are used for the treatment of tobacco products, the additive can, for example, be in a suitable Kind of taught by spraying, dipping, or otherwise. The pyrimidines can be used during the storage (casing) or added to a final spray treatment of the tobacco, or at any earlier stage in the treatment or preparation of the tobacco are applied.

The amounts of the pyrimidines or their mixtures used should be enough. to impart the desired flavor character to the treated product; on the other hand is however, the use of an excessive amount of pyrimidine is not only redundant and uneconomical, but in some In cases, too large an amount can lead to an imbalance in taste or other organoleptic properties of the product intended for consumption.

The appropriate amount to be used is determined by the final Food, tobacco product or other consumable

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Product depend; as well as the extent and type of taste originally present in the product after further processing or treatment to which the product is exposed; of regional or other preference factors; the type of storage of the product, if one is provided, and the treatment or preparation, such as baking, roasting, etc., carried out by End users before consumption. The terms effective amount and sufficient amount are accordingly in the context of the present invention as being quantitatively adequate for changing the taste of Understand food, tobacco, or other ingestible products.

Accordingly, it is preferred that the final composition be from about 10 ~ ° (10-9) ppm to about 200 ppm of the various Contains pyrimidines. In particular, from about 0.0001 to about 200 ppm is used in food mixes are desirable for flavor enhancement and in certain preferred embodiments of the invention, from about 0.01 up to about 20 ppm of the pyrimidines used in the end product for positive taste effects, on the other hand tobacco compositions, depending on whether cigarette tobacco, pipe tobacco, cigar tobacco, chewing tobacco or snuff are produced becomes as little as about 0.01 ppm or SQ viftl · as about Contains 100 ppm pyrimidines. The amounts of the various pyrimidines to be used will depend on many factors, including the specific compounds used, the desired taste, other ingredients present, the final use and the like.

The amount of oxacyclic pyrimidines or pyrimidines to be used in condiments can depend on the particular when it comes to food, tobacco or other consumable items

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Products to achieve quality over a wide range be changeable. Thus, amounts of one or more pyrimidines according to the invention of about 0.1 # to 80 or 90 # can be introduced. General becomes it is believed beneficial for about 0.5 to about 25 # pyrimidines to be present in such compositions.

The pyrimidines according to the invention, in particular thienopyrimidines can also be used individually or in the form of mixtures as fragrances. You can be used to teach a nut-like fragrance can be used. The thienopyrimidines according to the invention can be used as fragrances to form a "perfume composition" formulated or used as a component of such a perfume composition.

A perfume composition generally comprises a small but effective amount of pyrimidine according to the invention as well as perfume auxiliary 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 have a pleasant or desirable one Create fragrance.

Such perfume compositions usually contain: (a) Compounds which the main note or the "bouquet" determine the composition or make it up! (b) modifiers, which round off and accompany this main note j (c) Fixatives, which include fragrant substances that make perfume through all of them Levels of evaporation give a special note and substances that delay evaporation and (d) "top notes", which are usually caused by low-boiling points fresh smelling products are formed.

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In each perfume composition is used by the individual Components of their own special fragrance character contributed, the overall effect of the perfume composition then results from the superimposition of the individual effects of the components. Thus, the individual compounds according to the invention or mixtures thereof can be used to change the aroma characteristics a perfume composition, for example by increasing or refining or modifying the fragrance effect of other ingredients of the composition.

The amount of the compounds according to the invention which will prove 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 compounds according to the invention or even less, can be used to impart a pleasant fragrance to soaps, cosmetic articles and other products. The amount used can be as high as $ 50 or more and is determined taking into account the cost, nature of the end product, the expected effect, and the particular fragrance desired.

The thienopyrimidines according to the invention can be used alone or in a perfume composition as a fragrance component in washing powders, Cleaning agents and soaps are used as well as in air fresheners and deodorants, in perfumes and eau de Cologne, eau de toilette, bath preparations such as bath oil and bath salts, hair preparations such as varnishes, brillantines, pomades and shampoos, cosmetic preparations such as creams, deodorants, hand lotions and sunscreens; in powders, such as talc, Dust powder, face powder, etc. When used as a fragrance component of a perfumed product, small amounts of

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genes, such as about $ 0.01 of one or more pyrimidines are sufficient, to create a nut-like or seed-like odor. Generally no more than 0, j5 # are required.

In addition, the perfume composition or mixture of fragrances can be a carrier or a carrier for the pyrimidines Contained alone or with other ingredients. The carrier can be a liquid such as alcohol, glycol, or the like be. The carrier can be an absorbent or adsorbent solid, such as a rubber or slimy substance, or through Components for encapsulating the mixture are formed.

The following are examples to illustrate the invention in terms of presently preferred embodiments. These Examples serve for a better understanding and are in no way intended to restrict the invention in any way.

All parts, proportions, ratios and percentages given in the context of this description are, if nothing otherwise stated, based on weight.

Example I.

Preparation of 6,7-dihydro-5H-2-methyl ° cyclopenta-Cdi-pyrimidine

In a Parr hydrogenation apparatus 33.7 g of 4-chloro-6,7-dihydro-5H-2-methyl-cyclopenta-Cdl-pyrimidine, 150 ml of diethyl ether, 25 ml of water, 8.8 g of sodium hydroxide and 800 mg of a 5th # ig® ⁿ palladium catalyst given on charcoal. The hydrogen pressure applied at the beginning is allowed to drop from 2.3 at to 1.05 at, at which point the reduction is then complete. The sample is decanted from the apparatus removed di @ ether layer and the aqueous layer dr © i-

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times with 100 ml portions of ether extracted and the extracts united. After drying, the solvent is removed under reduced pressure, leaving 22.8 g of a white crystalline Pests remain behind. By recrystallization from hexane 16.0 g of 6,7-dihydro-5H-2-methyl-cyclopenta - [(i3-pyrimidine) are obtained. The melting point of this white crystalline pesticide is 55 ° C.

The nuclear magnetic resonance investigation (NMR) in deuterochloroform shows resonances at 8.4l (s; 1 proton); 2.94 (mj 4 protons); 2.69 (sj 3 protons) and 2.11 (m; 2 protons) ppm. Mass spectroscopy shows peaks at 134, 39, 106, 133, 42, 66 and 93 (order according to decreasing intensity),

The 6,7-dihydro-5H-2-methyl-cyclopenta- [jd3-pyrimidine has Sweet nut flavor notes of the crackers type with a roasted and nut-like roasted corn and whey character. It has also a very pleasant aftertaste of sweet milk.

This connection can be used in all areas of the visor, where sweet notes are desired, such as in milk spices, rice spices, breakfast food, sweet baked goods, vanilla flavorings and milk chocolate flavors.

The 6,7-dihydro-5H-2-methyl-cyclopenta- [el] -pyrimidine according to the invention with the 4-chloro-6,7-dihydro-2-methyl-5H-cyclopenta - [] cf | -pyriniidin U.S. Patent No. 2,969,361. When cyclopentapyrimidine according to the invention was a stronger roasted corn aroma than the known compound found as well as a highly desired milk-vanilla flavor, while the well-known compound has a very strong lingering one has a bitter aftertaste that drowns out its flavor notes and limits its use in flavorings. It

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has an effective visual wave at about 0.2 ppm and a scope in the region of 2 to 50 ppm.

Example II

Preparation of 4-methoxy-6,7-dihydro-5H-2-methylcyclopenta- jjdi-pyrimidine

100 ml of methanol are added to a 250 ml three-necked flask equipped with a reflux condenser, thermometer and magnetic stirrer to which 0.5 g (0.022 g atom) of sodium metal are slowly added with stirring until dissolved. Then a 4-chloro-6,7-dihydro-5H-2-methyl-cyclopenta-Cd ^ -pyrimidine portion of 5.0 g (0.018 mol) was added and the mixture was heated under reflux for two hours. The methanol will then Poured off from the sodium chloride and evaporated in vacuo. The remaining liquid-solid phase is twice with 25 ml Portions of diethyl ether extracted. The diethyl ether extracts are filtered and concentrated to a pink oil (2.8 g), then through a short path distillation apparatus is distilled under reduced pressure to obtain 2.21 g of a compound with a boiling point of about 67 ° C at 0.5 mmHg.

The NMR investigation (in deuterochloroform) shows resonances at 3.95 (s; 3 protons); 2.87 (mj 4 protons) j 2.57 (sj 3 protons) and 2.06 (mj 2 protons) ppmj by mass spectroscopy one finds peaks at m / e values of 164, I63, 149, 93, 65, 135 and 134 mass units (in order of decreasing relative intensity). These data confirm the formation of 4-methoxy-6,7-dihydro-5H-2-methyl-cyclopenta-Qr] -pyrimidine.

The 4-methoxy-6 _J 7-dihydro-5H-2-methyl-oyclopenta-

has burnt nuts and crackers notes with a pleasant sweet, fat nut character. It is for use in

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^A - 28 -

Crackers, nut products, nutrients, concentrated butter and tobacco flavorings suitable. It has an action threshold of 0.5 ppm and an application range of 2 to 80 ppm.

Example III

Production of 4-Ä * thoxy-6,7-dihydro-5H-2-methylcyclopentaplant pyrimidine

In a 250 ml three-necked semi-microreaction flask with The reflux condenser, thermometer, drying attachment and magnetic stirrer are added to 100 ml. Ethanol, to which 0.5 g (0.022 g atom) Sodium metal can be added slowly with stirring until the sodium has completely dissolved.

Then a 4-chloro-6,7-dihydro-5H-2-methyl-cyclopenta-jjä] -pyrimidine portion (5.0 g; 0.018 mol) is added and the mixture is heated under reflux for two hours. The solution is then cooled, the white sodium chloride precipitate is filtered off and the remaining solid-liquid phase is extracted with methylene chloride. The extracts to a yellow oil (2.8 g) and concentrated, which is then distilled in vacuo through a semi-micro short path distillation apparatus and 2.28 g of a very pale yellow liquid with a boiling point of 63-64 ⁰ C at 0.25 mmHg results.

The NMR investigation in deuterium chloride shows Resonances at 4.43 (q; 2 protons); 2.84 (m; 4 protons); 2.57 (s; 3 protons); 2.06 (m; 2 protons) and 1.36 (t; 3 protons) ppm; mass spectroscopy shows peaks at m / e values of: 178, I63, 150, 27, 149, 29 and 42 mass units (Order in decreasing relative intensity. The data confirm the formation of 4-ethoxy-6,7-dihydro-5H-2-methyl-cyclopenta- Pd] | pyrimidines.

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This 4-Kthoxy-6,7-dihydro-5H-2-methyl-cyclopenta- pyrimidine has nutty taste notes and is for nut spices and spices suitable for baked goods with an application range of 2 to 50 ppm and an action threshold of about 0.5 ppm.

Example IV

Preparation of 4-n-propoxy-6,7-dihydro-5H-2-methylcyclopenta-fd] pyrimidine

100 ml of n-propanol are placed in a 250 ml three-necked flask equipped with a reflux condenser, thermometer, drying attachment and magnetic stirrer, to which 0.5 g (0.022 g atom) of sodium metal are slowly added with stirring until the sodium is completely dissolved. Then a 4-chloro-6, T-dihydro ^ H ^ -methyl-cyclopenta- [cf | -pyrimidine portion (3.0 g; 0.018 mol) is added and the mixture is heated under reflux for two hours. The resulting mixture is cooled, the sodium chloride is filtered off and an amber-colored solution is obtained. The solution is concentrated in vacuo to remove the excess n-propanol and the product is then extracted with 25 ml portions of methylene chloride. The extracts are filtered and concentrated to a light brown oil (2.6 g). The oil is distilled through a Kurzwegdestillationsäpparatur under reduced pressure to yield 1.62 g of a colorless liquid having a boiling point of 8l to 83 ⁰ C at 0.15 mmHg.

The NMR study (in deuterochloroform) shows Resonances at 4.30 (t; 2 protons); 2.83 (m; 4 protons); 2.57 (s; 3 protons); 2.06 (m; 2 protons); 1.78 (m; 2 protons) and 1.00 (t; 3 protons) ppm; mass spectroscopy shows peaks at m / e values of: I92, 150, 149, I63, 27

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and 42 mass units (in order of decreasing relative intensity). These data confirm the formation of 4-n-propoxy-6, T-dihydro ^ H ^ -methyl-cyclopenta- £ d [] - pyrimidine

This link has sweet toasted nut aromas and is for crackers} bread, nut and meat sauce seasonings with one Suitable for an application range of 5 to 10 ppm and an action threshold of 0.5 ppsn.

Example V

Preparation of 4-isobutoxy-6,7-dihydro-5H-2-methyl - cyclopenta- ΕΠ-pyrimldine

In a 250 ml three-necked flask with a reflux condenser, thermometer, 100 ml of isobutanol are added to the drying attachment and magnetic stirrer, to which 0.5 g (0.022 g-atom) of sodium metal added slowly with stirring until the sodium has completely dissolved. A 4-chloro ^ -dihydro-SH ^ -methyl-cyclopenta-Qi ^ -pyrimidine portion is added (3.0 g; 0.018 Mo;) and heat the mixture under reflux 2 For hours. The resulting mixture is cooled, the sodium chloride is filtered off and the filtrate becomes a pale brown oil concentrated with a little pest. The connection is extracted from the excess sodium isobutoxide with 25 ml of methylene chloride and the methylene chloride solution then filtered and turned into a brown oil with a little pesticide concentrated (4.2 g), which is left to stand overnight. This Product is then distilled through a short path distillation apparatus and yields 1.46 g of a brown liquid with a boiling point of 77 ° C at 0.15 mmHg.

The NMR analysis (in deuterochloroform) shows reso-

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nances at 4.03 (dj 2 protons); 2.84 (m; 4 protons) j 2.56 (s; 3 protons); 2.05 (m; 2 protons) and 1.99 (d; 6 protons) ppm; mass spectroscopy shows peaks at m / e values of 206, 150, 149, 42, 41 and 65 mass units (in the Order of decreasing relative intensity). These data confirm the formation of 4-isobutoxy-6,7-dihydro-5H-2-methylcyclopentajjTJ-pyrimidine.

This compound has fruity, roasted fresh nut aromas with a slight butter-like aftertaste and is suitable for use in nuts, baked goods, sauces, meat and fruit spices with an application range of 2 to 100 ppm and has an action threshold of about 0.5 ppm.

Example VI

Preparation of 2-methylthio-6,7-dihydro-5H-oyclopenta-Cdl-pyrimldln

4.8 g (0.024 mol) of 4-chloro-2-methylthio-6,7-dihydro-5H-cyclopenta- (jd] -pyrimidine (prepared according to the method of Ross et al., J.Am.Chem.Soc. 81 »(I959) 3108-3114) and 250 ml of ethanol are added and the mixture is heated with stirring until it dissolves. 6.3 g (0.096 g-atom) of zinc dust are added to this solution and 0.64 g (0.012 mol) of ammonium chloride in 25 ml of water are added and the reflux treatment is started After one hour, two hours (addition of 0.65 g of ammonium chloride) and 4 hours (addition of 1.3 g of ammonium chloride), samples are taken The reflux treatment is stopped after 6 1/2 hours and the solution is left to stand for 2 days at room temperature, then 1.3 g of ammonium chloride are added

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- 52 -

and the reflux treatment resumed, an additional ,, borrowed amount of ammonium chloride of 1.3 g after 2 hours and 5 5/4 Hours added and the reflux treatment after 7 5/4 Stopped for hours and the solution stirred overnight. The resulting mixture is then concentrated to 50 ml and three times extracted with 50 ml portions of methylene chloride. The extracts are combined and dried by filtering through sodium sulfate and the filtrate 5 * 5 g of an amber Concentrated in the oil. This substance is then dissolved in 10 ml of hexane and filtered again and reduced to 5 * 0 g of a light yellow in vacuo Concentrated solid with a melting point of 48 ° C and a molecular weight of 166.

The NMR investigation (in deuterochloroform) gives Resonances at 8.3 (sj 1 proton); 2.86 (mi 4 protons); 2.54 (sj 3 protons) and 2.08 (m; 2 protons) ppm; mass spectroscopy peaks are found at m / e values of 166, 120, 59 * 165 and 65 mass units (in the order of decreasing relative intensity). These data confirm the formation of 2-methylthio-6,7-dihydro-5H-cyclopenta- £ d "J-pyrimidine.

This product has a plant and spruce needle aroma and -Taste with a bitter aftertaste. It is for vegetable spices in a range of 5 ppm and also for fragrance compositions suitable.

Example VII

Preparation of 4-n-propylthio-6,7-dihydro-5H-2-methyloyolopenta-CcÖ-pyriinidine

In a 250 ml three-necked flask with reflux condenser, thermo

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meter and magnetic stirrer are added 100 ml of ethanol and 0.90 g (0.022 mol) of sodium hydroxide and stirred to form a solution. A 1-propanethiol portion of 1 * 7 g (0.022 mol) is added and the mixture is ^{heated to 50 °} C. for 15 minutes and then mixed with 3.0 g (0.018 mol) of 4-chloro-6,7-dihydro-5H- 2-methyl-cyclopenta- [dj -pyrimidine was added and the mixture was heated under reflux for 2 hours. The solvent is then removed in vacuo and 25 ml of water are added and the solution is extracted three times with 25 ml portions of methylene chloride. The combined extracts are dried by filtration over sodium sulfate and concentrated to 3 * 8 g of an oil. The yellow oil is then distilled under reduced pressure through a short path distillation apparatus and gives 2.2 g of a yellow liquid with a boiling point of 99 to 101 ° C.

The NMR investigation (in deuterochloroform) gives Resonances at 3.18 (t; 2 protons); 2.78 (m; 4 protons); 2.60 (sj 3 protons); 2.06 (m; 2 protons); 1.72 (m; 2 protons) and 1.10 (t; 3 protons) ppm; mass spectroscopy there are peaks at m / e values of 208, 166, 175, 165, 65 and 39 mass units (in order of decreasing relative intensity). These data confirm the formation of 4-n-propylthio-6,7-dihydro-5H-2-methyl-cyclopenta-. £ cll-pyrimidine.

This compound has a weak sweet nutritional note * Example VIII

Preparation of 4-methylthio-6,7-dihydro-5H-2-methylcyclopenta-pQ-pyrimidine

In a 250 ml three-necked flask with reflux condenser, thermo

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meter and magnetic stirrer are 100 ml of ethanol and 0.9 g Added (0.022 mol) of sodium hydroxide, the solution was cooled to 0.5 ° C, treated with 1.1 g (0.022 mol) of methanethiol and the mixture was stirred at 0.5 ° C for 15 minutes. The mixture is then refluxed for two hours. Thereafter the solvent is removed under reduced pressure and 25 ml of water is added to the residue, which is then three times is extracted with 25 ml portions of methylene chloride. The United Extracts are dried by filtration through sodium sulfate and the filtrates are concentrated to give 3.1 g of a light yellow solid with a melting point of 48 ° C.

The NMR investigation (in deuterochloroform) gives Resonances at 2.8l (m; 4 protons); 2.63 (s; 3 protons); 2.56 (s; 3 protons) and 2.10 (m; 2 protons) ppm; mass spectroscopy peaks are found at m / e values of 180, 147, 65 * l65 * 106 and 39 mass units (in the order of decreasing relative intensity). These data confirm the formation of 4-methylthio-6,7-dihydro-5H-2-methyl-cyclopentajjcfj-pyrimidine.

This substance has Green Plants, pine needle and W nußähnliches aroma and taste appropriate.

Example IX

Preparation of 4-cyclopentylthio-6,7-dihydro-5H-2-methy1-cyclopenta-pf] pyrimidine

In a 250 ml three-necked flask with a reflux condenser, thermometer and magnetic stirrer, 100 ml of ethanol and 1.5 g (0.036 mol) of sodium hydroxide are added and stirred to form a solution. To this end, 3.7 g (0.036 mol) of cyclopentanethiol are added and the mixture is heated to 50 ° C. for 15 minutes

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and then with 3.0 g (0.018 mol) of 4-chloro-6,7-dlhydro-5H-2-methyl-cyclopenta- (jä ^ -pyrimidine added and the mixture was heated under reflux for 2 hours. The solvent is then removed in vacuo and 25 ml of water are added and the solution extracted three times with 25 ml portions of methylene chloride. The combined extracts are filtered off dried over sodium sulfate and added to 5.2 g of one amber-colored oil. This substance is distilled through a short path distillation apparatus in vacuo and gives 2.00 g of a very light amber colored liquid with a boiling point of 116 to 118 ° C at 0.15 mmHg.

The NMR investigation (in deuterochloroform) gives resonances at 4.17 (m; 1 proton)] 2.83 (m; 4 protons); 2.60 (sj 3 protons); 2.11 (m; 6 protons) and 1.67 (m; 4 protons) ppm; mass spectroscopy shows peaks at m / e values of 234, 166, 201, 41, 165 and 69 mass units (in the order of decreasing relative intensity). These data confirm the formation of 4-cyclopentylthio-6 _J 7-dihydro-5H-2-methylcyclopenta- £ d] pyrimidine.

This material has a pleasant sweet onion flavor with certain meaty notes and is for suitable for use in meat spices in the range of 5 ppm.

Example X

The following mixture was produced by refluxing for 3 hours and aging for 3 days:

Share L-cysteine hydrochloride

Carbohydrate-free vegetable protein hydrolyzate

Thiamine hydrochloride

Water 209809/1679

66 20th 23, 66 48 78

ZU1916

0.33 part of 6,7-dihydro-5H-2-methyl-cyclopenta- [cl3-pyriniidin are added to the above mixture and the resulting mixture using a sufficient amount of gum arabic spray dried. A composition is obtained with one part flavoring substances (pesticides) and one part Gum arabic.

After drying, the product has a taste that is closely reminiscent of natural beef.

Example XI

A black walnut flavor is made by mixing the following ingredients together:

Parts

vanilla 3 Heliotropin }: -: ■ p-cresyl phenylacylate te Ethyl valerate 5 Amyl valerate 5 p-cresyl methyl ether 5 Patchouli oil 2 Sage clear extract (10 #; 95 # alcohol) 2 Aldehyde (C: 14) 1 Aldehyde (C: 18) 1 Benzaldehyde 2 "Penugreek" plague extract ( Solid extract Fenugreek) (10 # in propylene glycol / water 1: 1) . 500 Propylene glycol 467

4-Isobutoxy-6,7-dihydro-5H-2-methyl-cyclopenta-Cd! I-pyrimidine 5

The use of 4-isobutoxy-6,7-dihydro-5H-2-methyl · 209809/1679

2U1916 - 37 -

Cyclopenta- [cQ-pyrimidine in amounts of $ 0.5 improves the nut-like character of this seasoning in such a way that it is closely reminiscent of natural black walnut Taste gives, and more than without the pyrimidine.

Example XII

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

Parts

vanilla 40 Ethyl vanillin 15th Benzodihydropyrone 5 Rum essence 5 Alcohol (95 #) 235 Propylene glycol 400 water 300 4-methoxy-6,7-dihydro-5H-2-methyl- cyclopenta-ßi ^ -pyrimidine 30th

The above spice is made into a prepared cow

mixture (6.25 x 10 % \ 1 oz / 100 lbs) added. After baking, the resulting cake has a sweet enhanced vanilla flavor with buttery notes, more than a cake made with prominent seasoning but without pyrimidine.

Example XIII

A cake spice is made by mixing the following ingredients together!

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_2U1916 - 38 -

Parts

ft

Vanilla 4o

Benzodihydropyrone 4

Rum Essence 5

Alcohol (95 #) 2J5

Propylene glycol 400

Water 300

4-Ethoxy-6,7-dihydro-5H-2-methylcyclopenta-jjTI-pyrimidine 30th

The above seasoning is added to a prepared cake mix (in amounts of 6.25 x 10 #J 1 oz / 100 lbs); after baking, the cake obtained has an excellent taste of sweet pastries and vanilla, namely more than a cake made with the above seasoning but without pyrimidine.

Example XIV

A confectionery filling was made from the following ingredients manufactured:

Parts

Peanut butter 300

ground sweet cracker flour 100

Confectionery sugar 200

Cooking fat 25

When adding 5 ppm of 4-ethoxy-6,7-dihydro-5H-2-methylcyclopenta- [jdj-pyrimidine a fuller, richer flavor character is obtained for the confectionery filling.

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Example XV

A commercially available peanut butter has a content of 5 ppm 6,7-dihydro-5H-2-methyl-cyclopenta-JjcQ-pyriniidin modified and the so modified peanut butter against a non-modified peanut butter (i.e. a Peanut butter without added pyrimidine) tested and compared a greater peanut flavor intensity was found in the latter.

Example XVI

. A butter Imitation Röstmaisgeschmaekskonzentrat with 4-cyclopentylthio-6,7-dihydro-5H-2-methyl-cyclopenta [-] ä] pyrimidine in amounts of 0.6 wt% is prepared by the following recipe:

Parts

Propylene glycol 10k, 5

2-acetylpyrazine 0.5

Benzylidene acetone 3 * 0

Cinnamaldehyde 4.0

Heliotropin 5.0

Valeric acid 6.0

Cinnamyl butyrate 9.0

Ethyl butyrate 10.0

Benzodihydropyrone 12.0

Vanillin 4o, O

Lactic acid 50.0

Butyric acid 100.0

Diacetyl 50.0

^ -Cyclopentylthio-ö, 7-dihydro-5H ~

2-methyl-cyclopenta- [cf | -pyrimidine 6.0

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Example XVII

A "corn chip" snack product is prepared as follows: The solution of Example XVI is sprayed onto mild flavored corn-based chips to approximate 0.04% by weight . The resulting product is then air dried and a butter, roasted corn taste and aroma is determined, so that the product is preferred over untreated chips.

Example XVIII

The following mixture was prepared by refluxing for 3 hours and aging for 3 days;

Parts

L-cysteine hydrochloride 66 Carbohydrate-free vegetable protein hydrolyzate 23.20 Thiamine hydrochlorld 66 water 78.48

0.33 parts of oiT-dihydro-SH-cyclopenta-Qfl-pyrimidine become added to the above mixture and the resulting mixture spray dried using a sufficient amount of gum arabic to achieve a mixture with one part flavorings (solids) and one part gum arabic.

After drying, the resulting product has a taste closely reminiscent of natural beef.

Example XIX Preparation of 2-methyl-5,7-dihydrothieno-D, 4-d '] - pyrimidln

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A mixture of 55.8 g of 2-methyl-4-chloro-5,7-dihydrothieno-j £ 5,4-d3-pyrimidine, 78.5 g zinc dust, 8.04 g ammonium chloride and 840 ml of 67 # ethanol is under for 2 hours Heated to reflux. After cooling, the insoluble material is removed by filtration.

The solid residue is three times with 300 ml of 95 # igem Washed ethanol and the combined filtrates concentrated to a volume of about 3OO ml. After adding 100 ml Water, the solution is extracted three times with 250 ml portions of methylene chloride. After drying, the solvent becomes removed in vacuo and crude 2-methyl-5> 7-dihydrothieno- £ 5 * 4-dJ-pyrimidine.

Chromatography on 820 g of silica and elution with 1 % methanol in methylene chloride and recrystallization from hexane mixed with decolorizing activated charcoal gives 17 g of pure 2-methyl-5,7-dihydrothieno- £ 5 _i 4-d '] - pyrimldine as short pale white needles that melt at 64.5 to 65 ^{° C.}

The mass spectral analysis shows a peak at an m / e value of I52 with peaks (in order of decreasing intensity) at 15I, 84, 39 and 124. (p + 8 / p + l) = p, 5. The nuclear magnetic resonance examination (in deuterochloroform) shows absorptions at 2.71 ppm which can be assigned to three protons; at 4.22 ppm, which is assigned to four protons, and at 8.54 ppm, which is assigned to one proton.

The scent of this pyrimidine in 0.1 # alcoholic Solution on a strip of blotting paper is a pungent smell of freshly roasted sweet nuts with a roasted corn Character. At this concentration, the scent seems to disappear as a result of Anosmle. In aqueous solution with 0.001 ppm the product has a sweet roasted nut and Röstijais

I U1 91 6

- 42 -

Character with a slightly astringent tendency. At 0.00? ppm in water it tastes like roasted corn and roasted peanuts with an astringency effect similar to peanut skin. At 10 ppm in chicken broth it enhances the root vegetable flavor "

It has also been found that the compound begins in a very low concentration in the region of 10 "^ ppm, the sweet Enhance the taste of food. At concentrations of 10 "· ^ ppm, it gives aqueous solutions a sweet, pleasant appearance not bitter aftertaste. It can act as a reinforcing substance to reduce the required amount of artificial Sweeteners can be used or it helps to decrease the amount of natural sweeteners such as sugar.

Example XX

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

component Quantity (parts) Methyl hexyl ketone 1.5 Diacetyl 14.2 Isovaleric acid 40.8 Hexanoic acid 158.9 Butyric acid 244.8 Caprylic acid 554.8 Thienopyrimidine according to Example XIX 5.0

The above cheese seasoning is used in mild cream cheese spread introduced and tried on crackers: the cheese spread had a good hot cheddar taste.

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Example XXI

A nut-like mass is made using conventional methods by mixing cottonseed oil, wheat germ, and cane sugar and glycerin made into a smooth paste and then mixed with fresh white egg. A is then added to the dispersion Seasoning mixture added, which contains the thienopyrimidine according to Example ΧΣΧ.

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

Example XXII

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 Phenyl ethyl 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

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2H1916

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

Connection parts

2-methyl-5,7-dihydrothieno-
£ 5,4-dj ~ pyrimidine 65

2,3> 5> 6-tetramethylpyrazine 35

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

Example XXIII

A perfume composition was produced by mixing the following ingredients:

component Quantity (parts) Geranium, bourbon 450 Patchouli 40 Vetivert (grass oil) 10 clove 100 Cinnamon (cassia) 30th Thienopyrimidine according to Example XIX 40 lavender 100 Orris resin 60

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2141918

Methyl! Onone 40

Coumarin 20

Musk, xylene 30

Terpineol 100

The above mixture is a fragrance composition from "transparent type". The thienopyrimidine is used as a replacement for parts of caraway essence, with the natural caraway note of the original perfume is preserved.

Example XXIV

A bread spice is made by mixing the following ingredients:

Connection parts

Lactic acid 50 acetic acid 20th Butyric acid 2 Propionic acid 5 Pyruvic acid Ethyl pyruvate 2 Isovaleraldehyde (10 ^ in propylene glycol) 2 Furfural 12th Benzaldehyde ($ 10 in Propylene Glycol) 2 2-methyl ~ 5,7-dihydrothieno- (3,4-d) -pypinii- din 2

100

The foregoing seasoning is added ₍₅ to a prepared bread dough flour asit "tartaric acid and sodium bicarbonate in slner Meng © \ ^Ton O.

2G $ 8G9 / 1g79

After baking, the resulting bread has an excellent appearance "Home-baked" cornbread flavor and appropriate Aroma characteristics as a result of the addition of the 2-methyl-5,7-dihydrothieno- (3,4-d) -pyrimidine.

Example XXV

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

Connection · parts

Maltol 2 Vanillin 12th Ethyl vanillin 3 Anisaldehyde (1 # in propylene glycol) 1 Propylene glycol 70 Ethanol (95 #) 12th 2-methyl-5,7-dihydrothieno- (3,4-d) -
pyrimldln
(O, lji 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.

Example XXVI

Preparation of 2-methyl-5,7- dlhydrofuro-D, 4-d'3-pyrimldine

a) Preparation of 2-methyl-4-hydroxy-5,7-dihydrofurop5,4-d3-pyrimidine

By adding 8.95 g (0.06 mol) of 3-C & rbmethoxyt «trahydrofwran-4-one, 5 ^ 95 g (0.063 mol) aoet & midin-hydroehlo-

2 U1 91 8 -4Y-

rid, 4.55 g (0.315 mol) potassium carbonate and 8? ml of 95 # ethanol a mixture is prepared which is left to stand at room temperature for 97 hours. Then the ethanol is im The vacuum is removed and the mixture is mixed with 10 ml of water and extracted three times with 10 ml portions of dichloromethane.

The extract is dried over sodium sulfate and filtered and the dichloromethane removed under reduced pressure. J5-carbmethoxy-tetrahydrofuran-4-one and by-products are separated off by vacuum distillation (74 to 90 ° / Q, 3 Torr), the residue that remains is recrystallized from benzene and 0.12 g of product is obtained.

The water-residue mixture is treated with 3 η sulfuric acid adjusted to pH 6, extracted three times with 10 ml portions of dichloromethane and yields on treatment as above an additional 0.07 g of product, so that the overall yield is 0.19 g of a solid with a melting point of 25% up to 257 ° C. The IR spectroscopy (Nujol) shows Ab, -sorptions at 5.92j 6.24j 6.32j 9.55l 10.9Oj Il, l6j 13.12 and 13.57 / Uj mass spectroscopy (70 eV) one finds peaks at m / e values of 151, 152, 124,% 2 and 55 mass units (in the order of decreasing relative intensity) ι die NMR spectroscopy (in deuterochloroform) gives resonances at 5.06 (2j tj J = 4 cpsj FTLh) J 4.90 (2j ts J-4 opsj FT ^) J

2.50 (3i s; / O> —GH ») ppm. These data confirm the formation of "2-methyl-4-hydroxy-5 _i 7-dihydrofuro- [3,4-of | -pyrimidine.

b) Production of 2-methyl-4-chloro-5,7-dihydrofuro «' £ 3,4-Ot] pyrimidine

A mixture of 0.17 S (0.00112 moles) of 2-methyl-4-hydroxy-5,7-dihydrofuro-p, 4-d3-pyrimidine and 1.0 ml of phos-

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2H1916 - 48 -

phosphorus oxychloride is refluxed for 110 minutes and then poured onto 10 g of ice. The mixture is first adjusted to pH 5 by adding 50 # strength sodium hydroxide solution and then brought to pH 6 by adding saturated sodium bicarbonate solution. The aqueous mixture is saturated with sodium chloride and extracted three times with 15 ml portions of dichloromethane. The extract is dried over sodium sulfate and filtered, and the dichloromethane is removed under reduced pressure and 0.12 g of residue is obtained. The sublimation of this residue at 0.1-0.5 torr at room temperature gives 25 mg Product.

The container residue is then chromatographed on silica gel with 1% methanol in dichloromethane as the eluent and gives 50 mg of product, so that the total yield is 75 mg of solid. Vapor phase chromatography of this material on Carbowax (20M) (trade name 0s Union Carbide Corporation for a series of polyethylene glycols) provides at 48 - 49 ⁰ C melting sample. Mass spectroscopy (70 eV) reveals peaks at m / e values of 170, I69, 142, 42, I06, 171, 172, 64, 107 * 66 and 144 mass units (in the order of decreasing relative intensity). This material is therefore verifiably 2-methyl-4-chloro-5,7-dihydrofuro-p, 4-d] -pyrimidine.

c) Preparation of 2-methyl-5,7-dihydrofuro-C3,4-d] pyrimidine

A mixture of 0.075 g (0.00044 moles) of 2-methyl-4-chloro-5 > 7-dihydro- {3,4-dJ-pyrimidine, 0.12 g (0.0018 mole) zinc and 0.025 g (0.00047 mole) ammonium chloride becomes one Added a mixture of 1.5 ml of 95 # strength ethanol and 0.5 ml of water and started the reflux treatment. After 3 hours will be in the 4th hour of the reflux treatment an additional 0.075 g

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2H1916 - 49 -

Ammonium chloride was added and, after refluxing for 5 hours, the mixture was cooled and filtered and the ethanol was removed under reduced pressure and 20 mg of residue were obtained. This residue is purified by chromatography on silica gel with dichloromethane and \% methanol in dichloromethane as eluents. "The solvents are removed under reduced pressure and 10 mg of product is obtained, which is further obtained by dissolving in 1 ml of fentane, filtering and separating off the pentane in vacuo is purified (yield: 10 mg of product). NMR spectroscopy (in deuterochloroform) shows resonances at 8.52 (1j sj ^ qV h); 5, 14 (2; s; U-H) i

4.98 (2; t; J = 2 cps. LL-H); 2.74 (3; s; fo ^ <%) ppm

and the mass spectroscopy (70 eV) peaks at m / e values of 136, 108, 42, 39 and 135 mass units (in the order decreasing relative intensity). The product is therefore verifiably 2-methyl-5,7-dihydrofuro- £ 5> 4rd]] pyrimidine.

This compound has a crackers, roasted corn and nut-like character and an aroma like sweet baked goods. It is suitable for use in nut spices.

Example XXVII

Preparation of 2,7-dimethyl-5j7-dihydrofuro-D, 4-dlpyrimidine

a) Preparation of 2,7-dimethyl-4-hydroxy-5,7-dihydrofuro- | [3,4-d} -pyrimidine

By adding 47.5 g (0.503 mol) of acetamidine hydroohlorld to sodium ethoxide in ethanol, which was prepared by adding 11.5 g (0.5 mol) of sodium to 270 ml of ethanol, a mixture is prepared ₉ which then 10 Minutes

2H1916

is stirred under nitrogen. 79 * 1 g are added to this mixture (0.5 mol) 2-methyl-4-carbmethoxy-tetrahydrofuran-3-one was added and the resulting mixture is kept at room temperature for 24 hours, after which the ethanol is separated in vacuo and 100 ml of water is added to the residue. The pH of the aqueous mixture is adjusted to 8 η hydrochloric acid adjusted to 7 and the mixture then extracted three times with 100 ml portions of dichloromethane. The extract is over Sodium sulfate dried, filtered and the diehlomethane removed under reduced pressure. The residue is triturated with hexane and filtered, yielding 6.5 g of crude product and the further extraction (seven times with 100 ml portions) of the aqueous layer with diehlomethane gives additional 4.4 g of crude product. Recrystallization of the crude product from carbon tetrachloride gives 5 # 2 g of a pesticide with a melting point of 190 to 203 ° C. IR spectroscopy (Nujol) shows absorptions at 5.95; 6.33; 7 * 60; 8.07; 8.63; 9.36; 9.67; 10.56; 10.72; 11.79; 12.32; 12.92 and l3i70 / U; the mass spectroscopy (70 eV) peaks at m / e values of 42, 151, I08, I66, 43, 39, 138 and 124 mass units (in order of decreasing relative intensity). The material is therefore 2,7-dimethyl-4-hydroxy-5,7-dihydrofuro-Jj5 * 4-d3-pyrimidine.

b) Preparation of 2,7-dimethyl-4-chloro-5,7-dihydrofuro-JTj, 4-dJ-pyrimidine

6.0 g (0.0361 moles) of 2,7-dimethyl-4-hydroxy-5,7-dihydrofuro-D 1-4 -dJ -pyrimidine are added to 24.0 ml (0.262 mol) of phosphorus oxychloride and the mixture for 135 minutes treated under reflux. About half of the phosphorus oxychloride is then removed under reduced pressure and the remaining Mixture poured onto ice. The resulting aqueous mixture is brought to pH 6 with 50 # strength sodium hydroxide solution

209809/1879

2 U 1 91 6

and then extracted three times with 100 ml portions of dichloromethane. The extract is dried over sodium sulfate and filtered, and the dichloromethane is separated off under reduced pressure and 6.4 g of crude product are obtained. This crude product is dissolved in a small amount of \% methanol in dichloromethane and passed through a column of 194 g of silica and eluted with 1% methanol in dichloromethane. The combined fractions yield 4.13 g of product after the solvent has been separated off under reduced pressure. The IR spectroscopy (NEAT) gives absorptions at 3.38; 3.44; 3.52; 6.24; 6.44; 7.08; 7.75; 9.24; 11.38 and 11.82 / u; NMR spectroscopy (in deuterochloroform) shows resonances at 5.28 to 5.08 (3; overlapping muffles;

H ^); 2.74 (3; s; <Q y ™ .CH ₃ ); 1.53 (3; d; J = 6 cps; ¹ H

Γ " 3) 1 PP ^m ·

Mass spectroscopy (70 eV) there are peaks at m / e values of 169, 17I, 43, l84 ₃ 42 _a 64, L4L, and 142 mass units (in order of decreasing relative intensity) This material is consequently the 2, 7 ~ Dimet] iyl- = 4-ehlor-5 _J 7-dihydrofuro-C3,4-d "] -pyrimidine,

c) Preparation of 2,7-diraethyl-5,7-dlhydrofuro-C3,4-d3-pyrimidine

By adding 0.58 g (0.0035 mol) 2 _{s of} 7-dimethyl-4-chloro-S ^ -dihydrofuro-p ^ -dJ-pyriraidin, 0.92 g (0.014 mol) zinc and 0.20 g ( 0.0037 mol) of ammonium chloride to a mixture of 9.0 ml of 95 # strength ethanol and 4.5 ml of water, a mixture is prepared and the reflux treatment is started. After 100 minutes of reflux, 0.4 g of ammonium chloride are added, after 240 minutes 0.5 g of ammonium chloride, after 280 minutes 0.5 g of zinc and after 380 minutes a further 0.2 g of zinc.

209809 / 1S79

2,916

After the reflux treatment has ended (410 minutes), the mixture is filtered and the ethanol is removed in vacuo and the residue dissolved in dichloroethane. This solution is dried over sodium sulfate, filtered and the solvent separated under reduced pressure to give a liquid residue (0.27 g) which can be identified by gas phase chromatography is purified on a Carbowax (20 M) column and yields the product.

The IR spectroscopy (NEAT) shows absorptions at 2.93; 3.38; 3.44; 3.52; 6.24; 6.36; 6.96; 7.09; 9.26; 9.56 and 11.71 / u; the NMR spectroscopy (in deuterochloroform) shows resonances at 8.50 (1; s; ^ ü>H); 5.16 to 5.08 (3; overlapping multiplets; ^^ LJ ^ _H 3); 2.75 (3; s; ^ Oj> - ° ^CH -3); 1.52 (3; d; J = 6 cps;

ppm. Mass spectroscopy (70 eV) shows peaks at m / e values of 135, 50, IO8, 107, 39, 42, 43, 52 and 79 mass units (in order of decreasing relative intensity). This Materia ^ is therefore the 2,7-dimethyl-5,7-dihydro furo- £ 3,4-dJ -pyrimidih.

This compound has a roasted corn and cracker aroma and is for use in sweet and salty baked goods suitable as well as for nut and vanilla spices.

Example XXVIII

Preparation of 2,5,7-trimethyl-5,7 dihydrofuro-C3,4-d3-pyrimldine

a) Preparation of 2,5 »7-trimethyl-4-hydroxy-5,7-dihydrof uro-f3,4-dJ | -pyrimidine

209809/1679

A mixture of 27.0 g (0.157 mol) of 2,5-dimethyl-3-carbmethoxy-tetrahydrofuran-4-one and 15 * 3 g (0.162 mol) of acetamidin hydrochloride is dissolved in 135 ml of 95% ethanol at room temperature. For this purpose, 11.2 g (0,08l mol) of potassium carbonate was added and the mixture allowed to stand at room temperature for 16 hours and then ¹ J hours heated under reflux again and allowed to stand at room temperature for 64 hours. The solvent is then removed in vacuo, 40 ml of water are added and the solution is adjusted to pH 7 with 4 η hydrochloric acid. The mixture is then extracted four times with 55 ml portions of dichloromethane, dried over sodium sulfate and filtered, and the solvent is removed in vacuo. The solid residue is triturated with carbon tetrachloride and filtered to give 5.2 g of a white solid. The mother liquor is then concentrated, cooled and filtered to give an additional 0.7 g of product so that the total yield is 5.9 g of product. IR spectroscopy (NuJoI) shows absorptions at 6.06; 7.62; 8.62; 9 * 41; 9.91; 10.68; 11.88; 12.57 and 13.36 / u; the NMR spectroscopy (in deuterochloroform) resonances at 5 * 44 to 4.98 (2; overlapping multiplets; ^ TJ ^ S 3) J

2.5i O,., ^> - ^c % ' ™ * ¹ ^ (ft * » ^J = ⁶ ° p ^s ' clQ "' ppm. Mass spectroscopy (70 eV) shows peaks at jn / e values of I65, 42, 43, 180, 124, 138, 137 and 96 mass units (in the order of decreasing relative intensity) .This product is therefore 2,5 * 7-trimethyl-4-hydroxy-5,7-dihydrofuro £ 5.4 -d3 ~ pyrimidine.

b) Preparation of 2,5,7-trimethyl-4-chloro-5,7-dihydrofuro- £ 5,4-dj-pyrimidine

A mixture of 4.50 g (0.0250 moles) of 2,5,7-trimethyl-4-20 9809/1679

hydroxy-5i7-dihydrofuro- |] 3,4-α3-pyrimidine and 18.0 ml (0.196 mol) of phosphorus oxy chloride are refluxed for 90 minutes. Then 16 ml of phosphorus oxychloride are removed in vacuo, the resulting thick residue is dissolved in 50 ml of chloroform and treated with 10 ml of water and then 12.6 ml of ammonium hydroxide, the temperature being kept below 40.degree. The pH of the mixture is then adjusted to 8, the salts formed are separated off and the aqueous phase is then separated off and extracted three times with 15 ml portions of chloroform. The combined extracts are dried over sodium sulfate and filtered, and the chloroform is removed under reduced pressure. The residue is triturated with hexane and filtered and the hexane is separated off in vacuo and 2.49 g of a liquid residue are obtained. This is chromatographed on 75 g of silica with dichloromethane as the eluent, the fractions are combined and the solvent is separated off under reduced pressure and 0.80 g of substance is obtained. TR spectroscopy (NEAT) shows absorptions at 5.40; 5 * 46; 5 * 52; 5 * 76; 6.28; 6.46; 7.07; 9.27; 10.6l; 11.04; 11.42 and 11.92 Ax% the NMR spectroscopy (in deuterochloroform) resonances at 6.52 to 5.04 (2; overlapping multiplets;

CH, 1 1 CH,. JZ TNv

H ^ h ->); 2.65 (5; s; J = 4 cps; ^ Q ^ - CH ₅ );

TT r " " f Tj

1.56 (6; overlapping doublets jtLvI L · ") ppm.

spectroscopically (70 eV) one finds peaks at m / e values of 185, 185, 45, 42, 78, 51, 52, 155, 147, 156, 59, * 1. 198 and 197 mass units (in decreasing order relative intensity). This material is therefore 2,5,7-trimethyl-4-chloro-5,7- <ühydrofuro-p, ^ -dj-pyrimidine.

c) Production of 2,5,7-trimethyl-5,7-dihydrofuro- £ 3,4-d] pyrimidine

209809/1879

A mixture of 0.70 g (0.0035 mol) of 2,5,7-trimethyl-4-chloro-5,7-clihydrofuro-p, 4-d] -pyrimidine, 0.92 g (0.0014 mol ) Zinc and 0.095 g (0.0018 mol) of ammonium chloride are added to a mixture of 7 * 0 ml of 95% ethanol and 4.5 ml of water and the reflux treatment is started. After 120 minutes of reflux treatment, 0.10 g of ammonium chloride and, after 180 minutes, 0.20 g of ammonium chloride are added. After the reflux treatment has ended, the mixture is filtered and the solvent and water are removed in vacuo and 0.42 g of product is obtained. The IR spectroscopy (NEAT) shows absorptions at 5430, 2960, 2890, 2840, 1599, 1580, 1450, 1432, 1410, IO74, IO23, 930, 891, 848, 797 and 761 cm "¹; the NMR spectroscopy ( in deuterium chloroform) resonances at 8.43 (Ij s; v / "X ^N \ tj) 5.50 to 4.94 (2; overlapping multi-

pletts; «UJ J ^ CH,) j 2.74 (3i

1.51 (6; d; J = 6 cps. HJ jLü) ppm.

Mass spectroscopy (70 eV) shows peaks at m / e values of 149, 43, 42, 164, 52, 121, 53, 150, 122, 51 and 163 mass units (in order of decreasing relative Intensity). This material is therefore 2,5,7-trimethyl-5, 7-dihydrofuro-Tj5,4-d} -pyrimidine.

This material has a sweet nutritional note. Example XXIX

A cake seasoning is made by mixing the following ingredients together:

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Parts

Vanilla 4o

Ethyl vanillin 15

Benzodihydropyrone 5

Rum Essence 5

Alcohol (95 #) 235

Propylene glycol 400

Water 300

2,7-dimethyl-5,7-dihydrofuro-

[3 * 4-d] pyrimidine 40

The above seasoning mixture is added to a prepared cake batter (6.25 x 10 "%; 1 oz / 100 lbs); the cake obtained after baking has an egg-like taste of sweet milk, more than one with the above seasoning but without pyrimidine manufactured cake.

209809/1679

Claims (1)

Patent claims /. Bicyclic pyrimidine derivatives of the general formula in which X stands for S, O or CH ₂ and R. a hydrogen or halogen atom or an alkyl, alkoxy, alkylthio or cycloalkylthio radical, R ₂ a hydrogen atom or an alkyl or alkylthio radical and R 1, R ₂ , R ₁ - and Rg, which can be the same "or different, denote hydrogen atoms or alkyl radicals, where R. and R _{2 are} not both intended to represent alkylthio radicals at the same time, as new flavorings. 2. 2-Methyl-5,7-dihydrothieno-C5,4-d] pyriniidine as a pyrimidine derivative according to claim 1. Cyclopentapyrimidines of the general formula , R 20§809 / 167 in which R _{1 is} an alkyl, alkoxy, alkylthio or cycloalkylthio radical or a hydrogen atom, R "is an alkyl or alkylthio radical and R ₁ , Rh, R 1 - and Rg, which can be identical or different, have hydrogen atoms or lower alkyl radicals 1 to 3 carbon atoms, where R. and R ₂ should not be alkylthio radicals at the same time, as pyrimidine derivatives according to claim 1. 4. Cyclopentapyrimidines according to claim 3 * characterized in that that the alkyl and alkoxy radicals 1 to £ carbon atoms, the alkylthio radicals 1 to 3 carbon atoms and the cycloalkylthio radicals Have 3 to 5 carbon atoms. 5 · Cyclopentapyrimidines according to Claim 3 »characterized in that R ,, Rj ,, R ₁ . and Rg represents hydrogen atoms, R _{2 represents} an alkyl radical and R- represents a hydrogen atom or an alkoxy, alkylthio or cycloalkylthio radical. 6. Cyclopentapyrimidine according to claim 5> characterized in that R. is a cyclopentylthio and R _{2 is} a methyl radical. 7. Oxacyclic pyrimidines of the general formula R ₂ ρ: $ ß η Q / in which R- denotes an alkyl radical or a halogen or hydrogen atom and Rp, R ,, Rj ,, R ₁ - and Rg, which can be identical or different, denote hydrogen atoms or alkyl groups as pyrimidine derivatives according to claim 1. 8. Oxacyclic pyrimidines according to claim 7 »characterized in that that the alkyl groups have 1 to 4 carbon atoms and the halogen atom is formed by a chlorine atom will. 9. Oxacyclic pyrimidines according to claim 7 *, characterized in that of the ligands R. to Rg Rp a methyl group or R ₀ and R-each a methyl group or R ₀ , dp c. R, and Rc each represent a methyl group, while each remaining ligands are formed by hydrogen atoms. Io. (»Acyclic pyrimidines according to claim 9, characterized shows that R is not a hydrogen but a chlorine atom 11. A process for the preparation of the bicyclic pyrimidine derivatives according to claim 1, in which X-S and R. to Rg, the may be the same or different, formed by hydrogen atoms or lower alkyl radicals having 1 to 5 carbon atoms are, characterized in that a halogen derivative of the corresponding pyrimidine by treatment with Zinc dust dehalogenated in the presence of an acidic substance. 12. A process for the preparation of the bicyclic pyrimidine derivatives according to claim 1, in which X ■ is -CH ₂ - and R. is an alkyl, alkoxy, alkylthlo or cycloalkylthio radical or a hydrogen atom, R _{2 is} a hydrogen atom or an alkyl or alkylthio radical and R ,, R ^, R_ and Rg, the same 209809/1679 - 6ο - or can be different, mean hydrogen atoms or lower alkyl radicals having 1 to j5 carbon atoms, where R. and Hp should not be alkylthio radicals at the same time, characterized in that the corresponding 4-halopyrimidine a) reducing under pressure in aqueous solution with a catalyst to the δ ^ -dihydro-SH-S-alkyl-cyclopenta-QfJ-pyrimidln dehalogenated, or b) with an alkali metal alkoxide to give 4-alkoxy-6,7-dihydro-5H-2-alkyl-cyclopenta- [cr | -pyrimidine etherified; or c) with an alkyl or cycloalkyl mercaptan in a solvent to the 4-alkylthio- or 4-cycloalkylthio-6,7-dihydro-5H-2-alkyl-cyclopenta-Cd ^ -pyrimidine implements. 13. A process for the preparation of oxacyclic pyrimidines according to Claim 1, in which R is an alkyl radical or a hydrogen atom and Rp, R ,, Rj ,, R ₁ - and Rg are identical or different and are hydrogen atoms or alkyl radicals, characterized in that one a carboalkoxytetrahydrofuran is reacted with acetamidine hydrochloride in the presence of a base and in a solvent to form an alkylhydroxy-dihydrofuropyrimidine, which is halogenated to give the alkylchlorodihydrofuropyrimidine and then dehalogenated in a reducing manner to give the corresponding alkyl-dihydrofuropyrimidine. 14. Use of the bicyolic pyrimidine derivatives according to claim 1 for seasoning and flavoring and for seasonings and fragrance compositions. 15 · Use of the bicyclic pyrimidine derivatives according to claim 1, in which X = S and R ₁ , Rg, R_, R ^, R ₅ and Rg 209809/1679 identical or different and hydrogen atoms or lower alkyl groups with 1 to 3 carbon atoms and in particular R _{2 is} a methyl group and R., R ,, R ^, R ₅ and Rg are hydrogen atoms according to claim 14 * 16. Use of the bicyclic pyrimidine derivatives according to claim 3, in particular according to claim 5 »according to claim Ik, 17. Use of the bicyclic pyrimidine derivatives according to claim 1, in which X = CH ₂ ; R ₁ , Ry R ^, R ₅ and Rg = and Rp are an alkylthio radical, according to claim 14. 18. Use of the bicyclic pyrimidine derivatives according to Claim 7 * in particular according to claim 8, according to claim 19. Use of the bicyclic pyrimidine derivatives according to claim 1, in which X = O, R ₂ = CH ^ and R ₁ , R ,, R ₂ ^, R, - and Rg = H, according to claim 14. 209809/1679