CH630512A5 - Organoleptic modifier - Google Patents

Description

60 The invention relates to an organoleptic modifier, i.e. a means of improving or intensifying the aroma or taste of consumer goods, such as foods, perfumes, perfumed articles, such as soap, detergents and cosmetic preparations, or of tobacco 65 or tobacco substitutes.

The organoleptic modifier according to the invention contains at least one compound of the formula (1) as active component

3rd

630 512

(1)

in which RA and Rc are the same or different and are methyl or hydrogen and RB is an alkyl or alkylthioalkyl group.

Preferred compounds of the formula (1) here are those of the formula (Ia)

(1a)

in which one of the groups Rl5 R2 and R3 is methyl and the others are hydrogen. Compounds of the formula (Ia)

2-alkyl-substituted 4,5-dimethyl-3-thiazolines are also mentioned below.

Likewise preferred as compounds of the formula (1) are those of the formula (Ib)

(1b)

in which Rn and R12 are the same or different and are hydrogen or methyl. The compounds (Ib) are also referred to below as 2-alkylthioalkyl-4,5-dialkyl-3-thiazo-15 line.

The compounds of formula (1) are obtainable by a process with the features of claim 2.

To prepare the compounds (Ia), an aldehyde or a ketone can be used as the compound of the formula (4) with 20 ammonia, preferably in aqueous solution, to give the corresponding imine of the formula (5) and then with a 2-mercapto-3-butanone react as a compound of formula (6) according to the following reaction scheme (A):

NH

(H2 °)

- »

R "

N

H

R.

R,

Ov SH

w

(1a)

Examples of this are given below. Suitable starting materials and reaction conditions are known per se from US Pat. Nos. 2,879,273 and 3,816,445 and DE-AS 1,095,284.

The compounds of the formula (Ib) are obtainable by first mixing an alkylthioalkanal as the compound of the formula (4) with aqueous ammonia to form the corresponding imine of the formula (5), which is then mixed with 45 3-mercapto-2- butanone or 3-mercapto-2-pentanone is reacted as a compound of formula (6) to obtain the desired thiazoline of formula (Ib). This reaction proceeds according to scheme (B) as follows:

R

12th

0

H

+ ™ 3 '(HO)

V £,

(lb)

The reaction parameters are discussed below and are generally described in U.S. Patent Nos. 3,816,445 and 2,879,273 (however, the substituent in the "2" position is the alkyl group and not the alkylthioalkyl group).

Older references, however, do not disclose the compounds (1), which have technical progress and unexpected advantages over the known. So be65

writes US Pat. No. 3,816,445 2-substituted A3-thiazolines as fragrances. You have the general formula

/ = N

O

\

R '

630 512

4th

wherein R 'and C ^ -Cj ^ alkyl group, which may be benzyl or 2-methylthioethyl. It is generally said that these compounds have “interesting vegetable notes, such as beans, tomatoes, pepperoni, asparagus and potato notes”.

In particular, compounds of the following formulas are disclosed:

and

For example, it is stated that 2-isobutyl-A3-thi-azoline has a “typical bean-like” wort with a “weak pepperoni note”.

Compounds of the general formula in which R'ls R'2, R'3 R'4 and R's can be hydrogen or an alkyl group are known from US Pat. No. 3,700,683 as intermediates for penicillamine syntheses. Furthermore, they are described in DE-AS 1 058 061.1 063 602 and 1 095 284 be-is. The same formula is mentioned in U.S. Patent No. 3,004,981.

Examples of compounds (1) are given below.

Table I

connection

Formula organoleptic properties

2- (2'-methylthioethyl) -4,5-dimethyl-A3-thiazoline

Sweet, fleshy, meat extract-like, meat broth-like, hydrolyzed vegetable protein-like, bread crust-like aroma with bread crust-like, sweet, monosodium glutamate-like, meat extract and meat broth-like, hydrolysed vegetable protein-like, salty, salty, metallic-smelling, salty, metallic-smelling, salt-like scents.

2- (2'-methylthiopropyl) -4,5-dimethyl-A3-thiazole

Sweet, meaty, meat extract and meat broth-like, potato-like aroma reminiscent of hydrolyzed vegetable protein, with sweet / meaty, meat extract and meat broth-like, metallic, salty and potato-like flavors reminiscent of hydrolyzed vegetable protein.

2- (2'-methylthioethyl) -4-methyl-5-ethyl-A3-thiazoline

Specific examples of 2-alkyl substituted 4,5-dimethyl-A3-thiazolines and their seasoning properties are summarized in Table II.

Sulfur-like, roasted and roasted meat-like, meat-broth-like, vegetable and tomato-like aroma with sulphurous, meat-broth-like, vegetable-like, metallic and taste and seasoning nuances reminiscent of cooked tomatoes.

Table!!

connection

formula

Spice properties

2- (2'-methylpropyl) -4,5-dimethyl-A3-thiazoline

Sweet, roast meat, reminiscent of roasted nuts, bitter chocolate-like aroma reminiscent of baked and green vegetables with a sweet, roast meat-like taste of roasted nuts, chocolate and hydrolysed vegetable-protein-like taste with a aftertaste reminiscent of hydrolysed vegetable protein and strong notes of chocolate.

5

Table II (continued)

630 512

connection

formula

Spice properties

2- (2'-n-butyl) -4,5-dimethyl-A3-thiazoline

Sweet, herbaceous, spicy, chocolate, nut-like and vegetable-like, roast-like aroma reminiscent of hydrolyzed vegetable egg, with herb-like, nut-like, roast and chocolate-like spice reminiscent of green vegetables and a strict character.

2-n-propyl-2,4,5-trimethyl-A3-thiazoline

The hydrolyzed vegetable protein distillate as prepared in Example 1 appears to contain the following A3 thiazoline derivatives:

2,4-dimethyl-A3-thiazoline;

4,5-dimethyl-A3-thiazoline;

2,4,5-trimethyl-A3-thiazoline; 2-propyl-2,4,5-trimethyl-A3-thiazoline; 2-ethyl-2,4,5-trimethyl-A3-thiazoline; 2- (2'-butyl) -4-methyl-A3-thiazoline; 2-n-butyl-4,5-dimethyl-A3-thiazoline; 2-benzyl-4-methyl-A3-thiazoline; 2,5-dimethyl-2-benzyl-A3-thiazoline; 2- (2'-methyl-n-propyl) -4,5-dimethyl-A3-thiazoline.

The presence of these compounds in the distillate of the refluxed hydrolyzed vegetable protein is detectable. The presence of these compounds in the distillate of hydrolysed vegetable proteins does not suggest that they can be used as seasonings for foods or to improve or intensify the flavor or aroma of foods.

When the 2-substituted 4,5-dialkyl-A3-thiazoline compounds according to the invention are used as seasoning adjuvants for food or to improve or intensify the seasoning or aroma characteristics of foods, the nature of those with the compounds as additional components also plays a role added substances plays a role and contributes to the organoleptic characteristics of the treated food.

“Improving” the seasoning characteristics of a food is understood to mean that seasoning is imparted to relatively mild and tasteless substances, or that existing seasoning properties, which are, however, relatively weak, are strengthened or their character and taste are changed.

“Intensifying” increases the spice or aroma character as well as the spice and aroma notes without changing the quality. This means that the existing wort is not given an additional note.

The term “food” is understood to mean both solid and liquid, edible or chewable, non-edible substances serving as food, for example chewing gum. These substances do not have to have any nutritional value. Examples include soups, conventional foods, beverages, gelatin desserts, dairy products, types of sugar, vegetables, cereals, non-alcoholic beverages. Sweet, green bean-like, cucumber-like, geranium-like and spicy aroma with cucumber-like, green bean-like, spicy, watermelon-like, black ones Pepper-like seasoning characteristics and a strict character.

ke, snack and the like.

25 additives or seasoning aids that can be used with the compounds (1) are known. Of course, they must have sufficient organoleptic tolerance, they must not be toxic or otherwise harmful. These substances include 30 in the broadest sense, stabilizers, thickeners, surface-active substances, conditioning agents, other seasonings and seasoning enhancers.

Stabilizers include preservatives such as sodium chloride; Antioxidants, for example calcium and sodium ascorbates, ascorbic acid, butylated hydroanisole (mixture of 2 and 3-tertiary butyl-4-hydroxyanisole), butylated hydroxytoluene (2,6-di-tert-butyl-4-methylphenol), Propyl gallate and the like, and sequestering agents, for example citric acid. 40 The thickeners include carriers, binders, protective colloids, suspending agents, emulsifiers and the like, for example agar agar, carrageenan; Cellulose and cellulose derivatives such as carboxymethyl cellulose and methyl cellulose; natural and synthetic gums, such as gum arabic, gum tragacanth; Gelatin, proteinaceous substances; Lipids; Carbohydrates, starches, pectins and emulsifiers, for example mono- and di-glycerides of fatty acids, skimmed milk powder, hexoses, pentoses, disaccharides, for example sucrose starch syrup and the like.

Surface-active or wetting agents include emulsifiers, for example fatty acids, such as capric acid, caprylic acid, palmitic acid, myristic acid and the like, mono- and diglycerides of fatty acids, lecithin, defoamer 55 and seasoning dispersants, such as conditioning agents include bleaching agents and agents which promote maturation, for example benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like, starch modifiers such as peracetic acid, sodium chlorite, sodium hypochlorite, propylene oxide, succin-6o anhydride and the like, buffering agents and neutralizing agents, for example sodium acetate, ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid, vinegar and the like Dyes, for example carminic acid, cochineal, curcuma and the like; Fortifying agents such as aluminum sodium sulfate, calcium chloride and calcium gluconate; Texturing agents, anti-caking agents, for example aluminum calcium sulfate and tri-basic calcium phosphate; Enzymes;

630 512

Yeast foods such as calcium lactate and calcium sulfate; Food additives such as iron salts such as ferric phosphate, ferrogluconate and the like, riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfate and the like.

Other seasoning additives and seasoning enhancers are: vanillin, ethyl vanillin, diacetyl, phenethyl 2-furoate, maltol, neryl butyrate, dimethyl sulfide. Linalool, acetic acid, methyl sulfide, acetaldehyde, isovaleraldehyde, isoamyl alcohol, acetic acid, lactones, isoamyl esters, including acetate, butyrate and octanoate, pyrazine, methylpyrazine, dimethylpyrazine, 2-ethyl-3-methylpyrazine, amyloctylanoate, isoamanoic acid 2-isoamyl acid octanoate, isoamyl acid octanoate, isoamanoic acid 2-isoamyl acid octanoate, isoamyl acid octanoate, isoamyl acid octanoate, isoamyl acid octanoate, isoamyl acid octanoate, isoamyl acid octanoate 2, for isoamyl acid octanoate, isoamyl acid octanoate, isoamanoic acid 2-isoamanoic acid 2-isoamino acid, isoamanoic acid-2-foro , Pyridine, phenylacetic acid, isobutyl-phenethyl alcohol, cinnamyl esters, such as the propionate, cinnamylphenylacetate, 4-phenyl-3-buten-2-one, 3-phenyl-2-pen-tenal, 3-phenyl-3-pentenal, 3 -Phenyl-4-pentenal, 3- (2-methylphenyl) -4-pentenal, 3-phenyl-4-methyl-4-pentenal, 2-phenyl-4-pentenal, 2-phenyl-4-pentenaldimethyl acetal, 2-isobutylthiazole, 2 (sec-butyl) thiazole, cocoa extracts, cocoa distillates, cocoa bean particles, bitter substances such as theobromine, caffeine and naringin, astringent agents such as tannin, quebracho and theotannates, and the like. These substances are mixed in appropriate proportions in order to achieve the effects described below.

The specific seasoning aids can be solid or liquid. The choice depends on the desired consistency of the end product, to which the 2-substituted 4,5-di-alkyl-A3-thiazolines are added and either dispersed in or mixed into this in order to obtain a homogeneous substance. The choice of one or more seasoning aids and the amount used also depend on the end product, and in particular on the desired organoleptic properties thereof. As a result, the choice of ingredients for the seasoning varies with the food to be seasoned. In the manufacture of solid products, such as bogus foods, substances are selected that are capable of normally producing solid products, for example different ones Cellulose derivatives.

The amount of the 2-substituted 4,5-dialkyl-A3-thiazolines used can vary within wide limits and depends in each case on the product to be seasoned and on the desired properties of the finished product.

However, there is no need to use too large quantities, even if these would not have an unfavorable influence, since a surplus causes additional costs. It is essential that the quantity is selected in a balanced framework and that a lower and an upper limit are observed.

It has been found that the 2-substituted 4,5-dialkyl-A3-thiazolines can be added in small amounts, for example about 0.1 to about 50 T / Mill., Based on the entire preparation. Quantities between about 0.2 to about 10 T / Mill have been the preferred range. proven. Larger amounts are not recommended as these s do not have an increased effect. In any case, care must be taken to ensure that a sufficient concentration of this compound is used when seasoning with a 2-substituted 4,5-dialkyl-A3-thiazoline.

Preferred seasoning compositions for food 10 contain the 2-substituted 4,5-dialkyl-A3-thiazoline in concentrations of about 0.1 to about 15% by weight, based on the total weight of the seasoning composition.

Conventional working methods, such as are customary for whipping batter and for producing fruit drinks, are suitable for producing the composition 15 described. The ingredients are mixed in appropriate proportions to obtain the desired consistency, a homogeneous dispersion, etc. In order to obtain the seasoning composition in the form of comminuted solids, the 2-substituted 4,5-dialkyl-A3-thiazo-lin can be e.g. Gum arabic, gum tragacanth, carrageenan and the like are mixed and the mixture obtained is spray dried, whereby a comminuted solid product is formed. Prefabricated seasoning mixtures in powder form, for example a fruit seasoning mixture, can be prepared by mixing the dry solids, for example starch, sugar and the like, and 2-substituted 4,5-dialkyl-A3-thiazoline in a dry mixer. Mixing is continued until the desired degree of uniformity is reached.

The following auxiliaries are preferably added to the 2-substituted 4,5-dialkyl-A3-thiazoline: acetaldehyde; Iso-butyraldehyde; Isovaleraldehyde; Dimethyl sulfide; Isobutylace-35 tat; Isoamyl acetate; Phenyl ethyl acetate; Diacetyl; Acetophe-non; Furfural; Benzaldehyde; Phenylacetaldehyde; Isoamyl alcohol; Phenylethyl alcohol; y-butyroIactone; 3-phenyl-4-pentenal; 3-phenyl-3-pentenal; 3-phenyl-2-pentenal; 2-methylpyrazine; 2,6-dimethylpyrazine; 2,3,5,6-tetramethylpyra-40 tin; 2,3,5-trimethylpyrazine; 2-ethyl-3-methylpyrazine; 2-ethyl-3,5-dimethylpyrazine; 2-ethyl-3,6-dimethylpyrazine; 2-ethyl-5-methylpyrazine; 2 (n-pentyl) thiazole; 2 (i-butyl) thi-azole; 2 (i-butyl) thiazole; 2 (i-propyl) thiazole; 2 (n-propyl) thi-azole; 2-phenyl-4-pentenal; 2-phenyl-4-pentenaldimethyllace-45 tal; Methional; 4-methylthiobutanal; 2-ethyl-3-acetyIpyrazine; trans-2-hexenal; Hydrolyzed vegetable protein; Monosodium glutamate; black pepper oil; Nutmeg oil, sel-lerie oil, lemon oil and mustard oil.

Specific examples of 2-alkyl substituted 4,5-di-50 methyl-A3-thiazolines which are useful in perfumery for perfumed articles and their properties therefor are listed in Table III below:

connection

formula

Perfume properties

2n-propyl-2,4,5-trimethyl-A3-thiazoline

Green aroma reminiscent of cucumber and dill, which has floral nuances when it dries out, reminiscent of natural tuberoses and sword lines.

2- (2'-Methylpropyl-4,5-dimethyl-A3-thiazoline

Excellent fresh, coffee-like aroma with deep green nuances.

7

630512

The 2-alkyl-substituted 4,5-dimethyl-A3-thiazolines of the formula in which Rj and R3 represent either the same or different substituents, namely hydrogen or the methyl group, are fragrances and can be incorporated into numerous compositions in order to To intensify or improve dill-, kaf-fee- and / or flower-, tuberous- or iris-like nuances.

The thiazolines can be added to the perfume preparations as pure compounds or in the form of mixtures in the compositions to be seasoned in order to give them the desired flavor of a finished perfume preparation. The perfume and seasoning preparations can be used in a wide variety of perfumed articles and are also suitable for intensifying, modifying or strengthening natural seasonings. It follows that the 2-alkyl-substituted 4,5-dimethyl-A3-thiazolines can be used both as fragrances and as seasonings.

“Perfume preparations” are understood to mean mixtures of compounds, which include, for example, the following substances: natural oils, synthetic oils, alcohols, aldehydes, ketones, esters, lactones, nitriles and often hydrocarbons that are mixed in, so that the combined fragrances of the individual components are one result in a pleasant or desired fragrance. Such perfume preparations usually contain (a) the main note or the “bouquet” or the cornerstone of the preparation; (b) modifiers that round off and accompany the main note; (c) fixatives, which include fragrances that give the perfume a special note throughout the time of evaporation, and substances that delay evaporation; and (d) top notes, which are usually low-boiling, freshly scented substances. The perfume preparations according to the invention can be used together with carriers, solvents, dispersants, emulsifiers, wetting agents, aerosol propellants and the like.

In perfume preparations, the individual components impart the special fragrance characteristics, but the overall effect is the sum of the effects of all components. Thus one or more of the compounds (I), i.e. 5 of the 2-alkyl-substituted 4,5-dimethyl-A3-thiazolines can be used to change, amplify, modify or intensify the aroma characteristics of a perfume preparation or a perfumed article, for example by emphasizing or weakening the fragrance other components of the preparation.

The effective amount of the 2-alkyl-substituted 4,5-dimethyl-A3-thiazolines in perfume preparations depends on several factors and not least on other components, their proportion and their effects. It has been found that only 0.005% by weight or even less of the compounds or mixtures can be used to impart intensely green and coffee-like or floral aroma notes to various cosmetic products, soaps or other preparations and products. The 20 quantities used depend on the cost, the nature of the end product, the desired effect of the finished product and the special fragrance. Up to 2% can also be added.

The thiazolines (1) can be used alone or together with a fragrance-changing or modifying compound, or in a perfume preparation as a fragrance in detergents (both anionic as well as cationic and nonionic detergents) and soaps. They are also suitable as room sprays, 30 perfumes, colognes, bath additives such as bath oil, bath salts, hair care preparations such as hair lacquers, brilliants, pomades and shampoos; cosmetic preparations, such as creams, deodorants, hand lotions, sunscreen preparations; Powders such as talc, face powder, body powder and the like. Amounts of 0.01% or less can be added. In general, it is preferred not to use more than 2% in the finished perfumed article since too much of the additive can affect the overall aroma and also unnecessarily increase the cost. 40 Specific examples of the compounds (1) which are suitable for improving or enhancing the aroma or taste of tobacco or tobacco substitutes, namely before and during smoking, are given in Table IV:

Table IV

connection

Formula organoleptic properties before smoking organoleptic properties during smoking

2- (2'-methyl-n-propyl) -4,5-dimethyl-A3-thiazoline

Chocolate, nut-like, sweet, bread-like, baked-like aroma and flavor

Sweet, nut and bread-like aroma with light green and light chocolate-like nuances

2- (2'-butyl) -4,5-dimethyl- * "•> = // Sweet, slightly green, nut- Slightly cool, slightly bread-

A3-thiazoline and bread-like aroma and like nuances when rough

^ J a similar wort

2- (2'-methylthioethyl) -4,5-dimethyl-A3-thiazoline

Fire aroma with a pleasant, slightly oily nuance

More aromatic tobacco-like aroma with greasy nuances

630512

The additives have been found to provide tobacco products with a flavor and aroma both before and during smoking that many smokers consider desirable. It should not be forgotten that the assessment of the character and quality of a tobacco product is very subjective. In any case, it was found that the compounds can give the tobacco various spice and aroma characteristics, which of course also depend on the substituents contained in the tobacco. After subjective tests, the additives give the tobacco products and their smoke flavor characteristics that smokers want, although the exact character cannot be described or defined with the known standard names.

Here too, one or more of the compounds (1) or their mixtures can be added to the tobacco, amounts of about 50 to 5000 T / mill., Based on the dry weight of the tobacco product, being used. The preferred amount is in the range of about 100 to 500 T / Mill. As usual, the amount required depends on the desired wort and aroma as well as the particular thiazoline.

The additive can be added during any stage of tobacco treatment. A concentrate can also be produced and then mixed in before the end product, such as cigarettes or other smoking articles, is finished. In this case, the quantities are also adjusted according to the end product.

In one embodiment, an aged, hot-dried and cut tobacco is made with a 1% alcoholic solution from a 40:40:20 (weight: weight: weight) mixture of 2- (2'-methyl-n-propyl) -4 , 5-dimethyl-A3-thiazoline: 2- (2'-n-butyl) -4,5-dimethyl-A3-thiazo-lin: 2- (2'-methylthioethyl) -4,5-dimethyl-Ä3-thiazoline sprayed in an amount to give a tobacco that was 10OT / Mill. (Weight) of the additive from thiazoline mixture on a dry basis. The alcohol is then evaporated and the tobacco is processed into cigarettes using conventional methods. It was found that these cigarettes had a desired and pleasant spice and flavor, which some smokers referred to as "nut-bread-like" and are very similar to "light" tobacco. The aroma is noticeable both in the main stream and in the side streams when the cigarette is smoked.

The additives can be added to the tobacco by spraying, dipping or in any other way using appropriate suspensions or solutions of the thiazolines. Water or volatile organic solvents such as alcohol, ether acetone, volatile hydrocarbons and the like, which can serve as carrier media, are suitable. Other seasoning and aroma additives can also be added, for example: (a) esters such as ethyl butyrate, ethyl acetate, ethyl valerate, amyl acetate, phenylethyl isovalerate and methylheptyl carbonate; (b) aldehydes such as 3-phenyl-2-pentenal, 3-phenyl-3-pentenal, phenylacetaldehyde, cinnamaldehyde and β-ethylcinnamaldehyde; (c) ketones such as benzylidene acetone; Acetophenone, maltol, and ethyl maltol; (d) acetals such as 3-phenyl-4-pentenaldimethyl acetal and 3-phenyl-4-pentenaldiethyl acetal (described in U.S. Patent 3,922,237); (e) natural oils and extracts such as vanilla, coffee extract, origanum oil, cocoa extract, clove oil, nutmeg oil, celery seed oil, bergamot oil and ylang-ylang oil; (f) lactones such as 8-decalactone, 8-un-decalactone, y-dodecalactone, y-undecalactone and coumarin; (g) ethers such as dibenzyl ether, vanillin and eugenol; (h) pyrazines such as 2-acetylpyrazine, 2-acetyl-6-methylpyrazine, 2-ethylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine and 2-ethyl-5-methylpyrazine; (i) pyroles such as N-cyclopropylpyrene and N-cyclooctylpyrene; as well as additives such as those described in US Pat 051 and 3 380 457 and in Austr. PS 444 545, 444 507 and 444 389 are disclosed.

The additives are particularly suitable for the treatment of cigarette tobacco, but can also be used for pipe or cigar tobacco or for other tobacco products. Likewise, tobacco substitutes of natural or artificial origin that are used for smoking or other ingestion can also be treated. They can consist of parts of tobacco plants or substitutes or both - for example, lettuce leaves or cabbage leaves-15.

In addition, the additives can also or only be added to the cigarette paper or the cigar sleeve or incorporated into the filter tip, the packaging material or the seam paste for gluing the cigarette paper. The following embodiments illustrate some preferred embodiments, which are by no means exhaustive.

example 1

25 Preparation of a reflux distillate of hydrolyzed vegetable protein

5 were placed in a 22 liter round bottom flask equipped with a heating jacket, air-driven cooler, a 4 x 57 cm covered column, filled with 3.175 mm glass screw, magnetically controlled return insert head and a 1 liter filling funnel kg of Nestlé 4BE hydrolyzed vegetable protein and 101 distilled water. The reaction mixture was heated to reflux and the reflux was started with a “draw-off” rate of 20%. 35 2 liters of distillate were collected and extracted with diethyl ether. The ether extract was concentrated to 100 ml and fractionated into acidic, phenolic, basic and neutral components. Each of the fractions was examined by gas-liquid chromatography, NMR, MS and IR 40 analyzes. The following thiazolines were found:

2,4-dimethyl-A3-thiazoline;

4,5-dimethyl-A3-thiazoline;

2,4,5-trimethyl-A3-thiazoline;

45 2-propyl-2,4,5-trimethyl-A3-thiazoline; 2-ethyl-2,4,5-trimethyl-A3-thiazoline; 2- (2'-butyl) -4-methyl-A3-thiazoline; 2-n-butyl-4,5-dimethyl-A3-thiazoline; 2-benzyl-4-methyl-A3-thiazoline; so 2,5-dimethyl-2-benzyl-A3-thiazoline; 2- (2'-methyl-n-propyl) -4,5-dimethyl-A3-thiazoline.

Example 2

Preparation of 2- (2'-methyl-n-propyl) -4,5-dimethyl-55 A3-thiazoline

Reaction scheme A, R1 = methyl, R2 = R3 = H.

45 ml of water and 45 ml of 58% strength aqueous NH 3 were filled into a 500 ml three-necked round bottom flask equipped with a stirrer, 250 ml filling funnel, ice bath and Fredericks cooler. With stirring, 43 glsobutyraldehyde were added dropwise. Then 104 g of a 50% ethanolic solution of 3-mercapto-2-butanone was added dropwise over a period of one hour. The reaction mixture was stirred at room-65 temperato for 1 hour.

The product obtained was extracted with three 100 ml portions of diethyl ether. The ether extracts were combined and dried over anhydrous sodium sulfate.

9

630 512

net and then evaporated in a rotary evaporator. The product obtained was distilled on a 12 "Vigreux column at 4 mm Hg pressure and 70 ° C. steam temperature and a product was obtained which had 97% 2- (2'-methyl-n-propyl) -4,5-dime- contained thyl-A3-thiazoline.

Example 3

Preparation of 2- (2'-n-butyl) -4,5-dimethyl-A3-thiazoline Reaction Scheme A (R = Methyl; Rj = R3 = H)

87.4 ml of 30% aqueous ammonia and 45 ml of distilled water were introduced into a 500 ml three-necked round-bottomed flask equipped with a mechanical stirrer, 250 ml filling funnel, thermometer, Fried-rich's cooler and ice bath. Then 43 g of 2-methylbutanal was added dropwise while the reaction mixture was kept at room temperature. After the addition of

2-Methylbutanal, 104 g of a 50% (in 95% ethanol) solution of 3-mer captobutanone was added dropwise over one (1) hour. The reaction mass was extracted with 300 ml of diethyl ether in three (3) portions. The ether extracts were combined and dried over anhydrous sodium sulfate and evaporated on a «rotovap». The product obtained was distilled at an evaporation temperature of 105 to 107 ° C and a vacuum of 20 mm Hg, whereby a product was obtained, the 98% 2- (2'-n-butyl) -4,5-dimethyl-A

3-thiazoline contained. Distillation was carried out on a 12 "Vigreux column. The product was purified at 60 to

61 ° C and a pressure of 3 mm Hg distilled again.

The product obtained existed in two (2) isomeric forms, namely the «endo» and the «exo» form.

Example 4

Preparation of 2,4,5-trimethyl-2-n-propyl-A3-thiazoline Reaction Scheme (A); Rt = R2 = H; R3 = methyl. 45.2 ml of a 58% aqueous NH3 solution and 45 ml of distilled water were introduced into a 500 ml three-necked round bottom flask equipped with a mechanical stirrer, 250 ml filling funnel, thermometer, Fried-rich's cooler and ice bath. To this mixture, 43.05 g of 2-pentanone was added dropwise from the hopper with stirring while the temperature of the reaction mixture was kept between 25 and 28 ° C. After the 2-pentanone addition was complete, 104 g of a 50% solution (in 95% ethanol) of 3-mercapto-2-butanone were added over one (1) hour while stirring, the reaction mass being kept at room temperature. The reaction mixture was extracted with three (3) 100 ml portions of diethyl ether and the ether extracts combined. These extracts were then washed with two (2) 100 ml portions of water, the ether extracts dried over anhydrous sodium sulfate and then evaporated on a rotary evaporator. The product obtained was distilled at a steam temperature of 104 ° C and a pressure of 31 mm Hg.

Example 5

A commercial cocoa blend was used to make two different approaches to drinks. The first batch was evaluated without any further addition of an additive, during the second batch a 2- (2'-methyl-n-propyl) -4,5-dimethyl-A3-thiazoline, prepared according to Example 2, in an amount of 40 mg per kg of cocoa drink was added. The drink without additives gave a rather strict impression, while the drink with the additive had a fuller, richer sweet milk chocolate spice.

Example 6

A basic preparation of a chocolate spice was made from the following ingredients:

Compound quantity in g

Dimethyl sulfide 1.0

Isobutyl acetate 1.0

Isoamyl acetate 1.0

Phenyl ethyl acetate 0.5 diacetyl (10% in 95% undenatured

Alcohol) 0.5

Furfural (50% in propylene glycol) 0.5

Isoamyl alcohol 1.0

y-butyrolactone 5.0

Acetophenone 0.5

Benzaldehyde 1.0

Phenylacetic acid 2.0

Maltol 3.0

Acetaldehyde 2.0

Isobutyraldehyde 8.0

Isovaleraldehyde 15.0

Phenylethyl alcohol 8.0

Vanillin 15.0

Propylene glycol 40.0

The seasoning mix was divided into two portions. 2- (2'-Methyl-n-propyl) -4,5-dimethyl-A3-thiazoline was added in an amount of 2% to a first portion. The second portion remained unchanged. The two samples were compared with each other, 5 T / Mill. were examined in water. It was found that the sample containing the seasoning mixture according to the invention had a more characteristic cocoa powder note, both in aroma and taste, so that this sample was preferable to the others.

Example 7

The following walnut preparation was produced:

Ingredients parts by weight

A flavoring known under the designation Cyclotene (2-hydroxy-3-methyl-

2-cyclopenten-l-one) 4

Vanillin 2

Butyl isovalerate 0.5 cuminaldehyde (10% in undenatured

95% ethyl alcohol) 0.5 2,6-dimethoxyphenol (10% in undenatured 95% ethyl alcohol) 0.5 benzaldehyde 8 2,3-diethylpyrazine 2 ethyl-2-methylbutyrate 0.5 y-butyrolactone 20 y-hexalactone 12 Benzyl alcohol 15 propylene glycol 35

This preparation was divided into two portions. To one of the portions was added 2- (2'-methyl-1-propyl) -4,5-dimethyl-A3-thiazoline in an amount of 8%. The second portion remained unchanged. The two samples were compared using an amount of 8 T / Mill. has been used. The inspectors were all of the opinion that the sample mixed with the thiazoline derivative gave a more characteristic walnut kernel impression, namely with the astringent notes inherent in the walnut shell.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

630 512

10th

Comparative experiments were carried out with a commercial ice cream with a vanilla flavor. Samples of this ice cream were each at 15 T / Mill. of the two walnut seasonings. It was found that the spice mixture containing the thiazoline derivative gave the ice cream a far better taste similar to walnut kernels than the simple preparation without thiazoline.

Example 8

A seasoning preparation was prepared by mixing the following ingredients:

Compound quantity in g

2-methylpyrazine 6 2,6-dimethylpyrazine 15 2,3,4,6-tetramethylpyrazine 12

3-Phenyl-4-pentenal 1 50/50 (w / w) mixture of

2- (2'-methyl-n-propyl) -4,5-dimethyl-A3-thiazoline and 2-n-propy-2,4,5-trimethyl-A3-thiazoline 4

This mixture was added to a chocolate milk that had a weak and thin flavor. An addition of 30 mg / kg increased the sweet milk chocolate and nut-like notes, and the additional addition of 40 mg / kg of the basic preparation of the cocoa seasoning as described in Example 6 gave the chocolate milk an excellent cocoa seasoning and Aroma note.

Example 9

0.10 T / Mill 2- (2'-n-butyl) -4,5-dimethyl-A 3-thiazoline was added to a portion of an essentially tasteless salad dressing. The mixture obtained had a characteristic cucumber, spiced marinade note. The salad dressing consisted of the following components:

Components parts

Black pepper oil 3

Nutmeg oil 3

Celery oil 3

Lemon oil 3

Mustard oil 1

Wine vinegar-citric acid (50:50) 120 starch paste made from tapioca

Flour-water (50:50) 300

Liquid egg yolk 210

Sodium chloride 7

Sugar 10

Mustard 20

Carob gum 6

Example 10

Preparation of 2 (2'-methylthioethyl) -4,5-dimethyl-

A3-thiazoline reaction scheme B, Rlt = methyl; R12 = H.

45.2 ml of a 58% aqueous ammonia solution and 45 ml of distilled water were introduced into a 500 ml three-necked runk flask equipped with a mechanical stirrer, 250 ml filling funnel, thermometer, Fried-rich's cooler and ice bath. For this purpose, 52 mg of methional were added with stirring, the temperature being kept at 25 to 28 ° C. Then 104 mg of a 50% solution of 3-mercapto-2-butanone in 95% ethyl alcohol were added dropwise with stirring over an hour. During the addition, the reaction mass was kept at room temperature. The mixture was extracted with two 100 ml portions of diethyl ether and the ether extracts were combined. It was then washed with three 100 ml portions of distilled water and the mass was dried over anhydrous sodium sulfate. The dried extracts were then evaporated on a rotary evaporator and the oil obtained was distilled on a 6 "Vigreux column and a steam temperature of 97 to 103 ° C, the liquid temperature being 129 to 140 ° C and the pressure 2 mm Hg be-io.

Example 11

Preparation of 2 (2'-methylthiopropyl) -4,5-dimethyl-A3-thiazoline

Reaction scheme B, Rn = H, R12 = methyl 15 87 ml of a 30% aqueous ammonia solution were filled into a 500 ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer, Friedrich's cooler, 250 ml filling funnel and ice bath this cooled to a temperature between 13 and 17 ° C. 59.1 g of 3-methylmethional were added dropwise with stirring. The reaction mass was stirred for 90 minutes and then 106 g of a 50% solution of 3-mercapto-2-butanone (in 95% ethyl alcohol) was added dropwise over 30 minutes. During the addition, the reaction mass 25 was kept at a temperature between 11 and 16 ° C. Thereafter, heating up to 25 ° C. was allowed and stirring was continued for a further 2 hours. The reaction mass was poured into a separatory funnel and two phases were observed, namely an oily and an aqueous phase. The oil phase 30 was drawn off and the aqueous phase was extracted with three 100 ml portions of diethyl ether. The ether extracts and the oil phase were combined and dried over anhydrous sodium sulfate. The solvent was removed on a rotary evaporator. The product was distilled on an 8 "Vigreux column at a steam temperature of 100 to 104 ° C and a pressure of 2 mm Hg.

Gas-liquid chromatography, NMR, IR and MS analyzes confirmed a compound of the following formula:

Example 12

Preparation of 2- (2'-methylthioethyl) -4-methyl-5-ethyl-A3-thiazoline

Reaction scheme B, R11 = methyl, R12 = H.

145.8 ml of a 30% aqueous ammonia solution were placed in a 1 liter reaction flask equipped with a mechanical stirrer, Friedrich's cooler, thermometer, isopropanol / dry ice bath and 250 ml filling funnel. The solution was kept at 5 to 15 ° C and 105.5 g of methional was added dropwise with stirring over 45 minutes. 253.9 g of a 50% 3-mercapto-2-pentanone solution (in 95% aqueous ethyl alcohol) were then added over 2 hours, the reaction mixture being kept at 10-15 ° C. 60 After the 3-mercapto-2-pentanone addition had ended, the temperature of the reaction mixture was allowed to rise to 25 ° C. and was kept at this level with a stirrer for 1 hour. The mass was then placed in a separatory funnel and 100 ml of a saturated 65% aqueous sodium chloride solution were added. Two phases were formed, namely an oil phase and an aqueous phase. The oil phase was separated from the aqueous phase and the latter with three 200 ml portions of Di-

extracted ethyl ether. The ether extracts and the oil phase were combined and washed with two 100 ml portions of saturated aqueous sodium chloride solution. The organic phase obtained was then dried over anhydrous sodium sulfate, freed of ether on a rotary evaporator and distilled on a 12 "Vigreux column at 174 ° C. and 22 mm Hg pressure.

The gas-liquid chromatographs as well as the NMR, IR and MS analyzes confirmed the connection of the formula

This substance has a threshold of 0.005 T / Mill. and a use value at a concentration of 0.01 T / mill., which gave a sulphurous, roasted, roasted meat-like, meat broth-like, vegetable and tomato aroma with a sulfurous meat-broth-like, vegetable, metallic and boiled tomato-like flavor becomes.

Example 13

A walnut wort was made by mixing the following ingredients.

Ingredients parts by weight

Vanillin 4.0

Ethyl 2-methylbutyrate 1.0

Butyl isovalerate 4.0

2,3-diethylpyrazine 0.5

Methylcyclopentenolone 8.0

a-Hydroxy-β-methyl-A, a, β-Y-hexenolactone 2.0

Benzaldehyde 6.0 Valerian oil Indonesia (0.1% solution in propylene glycol) 0.5

Propylene glycol 74.0

The walnut wort was in an amount of 10 T / Mill. compared in water with the same wort, but with 0.5 parts of 2 (2'-methyl-ethyl) -4-methyl-5-ethyl-A3-thiazoline, prepared according to Example 12, was added. The sample with the additive had a fuller, natural walnut kernel-like taste due to the addition of the thiazoline.

Examples 14

A walnut wort was made by mixing the following ingredients:

Ingredients parts by weight

Vanillin 4.0

Ethyl 2-methylbutyrate 1.0

Butyl isovalerate 4.0

2,3-diethylpyrazine 0.5

Methylcyclopentenolone 8.0

a-Hydroxy-ß-methyl-A-a, ß-y-hexenolactone 2.0

Benzaldehyde 6.0 Valerian oil Indonesia (0.1% solution in propylene glycol) 0.5

Propylene glycol 74.0

This walnut wort was in an amount of 10 T / Mill. compared in water with the same wort, but with 2% of the 2- (2'-methylthioethyl) -4,5-dimethyl-A3-thiazoline, prepared according to Example 10, was added. The latter sample had a sweeter, more walnut-

630 512

core and rounded taste and therefore turned out to be better.

Example 15

5 Vegetable seasoning preparation

A 2- (2'-methylthioethyl) - prepared according to Example 12

4-methyl-5-ethyl-A3-thiazoline was added directly to a food product before it was processed and canned. The seasoning effect of the thiazoline was very good, as the following information shows. The thiazoline was added to various food products just before they were consumed.

(i) In a vegetable sauce mixture in an amount of about 30 T / Mill .: The seasoning brought the note of

15 boiled vegetables with nuances of tomatoes.

(ii) In vegetable soup in an amount of 40 T / Mill .: the seasoning gave the soup the character of cooked vegetables and the cooked seasoning notes gave the whole vegetable seasoning more fullness.

2o (iii) In bean tomato sauce in an amount of about 20 T / Mill .: The seasoning changed the character by softening the strict note of the tomato seasoning mix and at the same time giving or developing notes of the cooked vegetables and «cooked» tomatoes.

25 The concentration of 2 (2'-methylthioethyl) -4-methyl-5-ethyl-A3-thiazoline produced according to Example 12 can be reduced by 25% when 2-isobutylthiazole in an amount of 5 T / Mill. is used with. At other concentrations there may be noticeable differences in the wort

30 are found.

Example 16

Use of 2- (2'-methylthioethyl) -4-methyl-5-ethyl-A3-thiazoline to increase the vegetable seasoning

35 of vegetarian vegetable soup

There were 2 T / Mill. 2- (2'-methylthioethyl) -4-methyl-

5-ethyl-A3-thiazoline, prepared according to Example 12, added to condensed vegetarian vegetable soup (commercially available under the Shop-Rite® brand). To 1 liter

40 soup, 1 liter of water was taken and mixed thoroughly. The mixture was boiled at about 93 ° C for 10 minutes. The soup obtained was compared to a soup sample which did not contain 2- (2'-methylthioethyl) -4-methyl-5-ethyl-A3-thiazoline. It was unanimously determined that the

45 a soup sample mixed with the seasoning additive was preferable because it had a more vegetable-like taste with a fuller mouthfeel and a better aroma, and even more pleasant nuances reminiscent of cooked tomatoes.

see example 17

A pulpy wort was made by intimately mixing the following ingredients:

Parts by weight

2.0 3.0 3.0 5.0 10.0

30 900

65 The addition of 2- (2'-methylthiopropyl) -4,5-dimethyl-À3-thiazoline to the mixture gave it an excellent shade reminiscent of baked potatoes, which is suitable for seasoning a commercially available potato pulp.

Components

Vanillin diacetyl butyric acid acetylmethylcarbinol so methional 2- (2'-methylthiopropyl) -4,5-dimethyl-

A3-thiazoline 95% undenatured ethyl alcohol

1

630512

12

The seasoning mixture is in an amount of 5 T / Mill. (A3-thiazoline: 0.15 T / Mill.) Used.

Example 18 Narcissus Perfume Preparation The following ingredients were mixed together:

Ingredients parts by weight

2- (2'-methylpropyl) -4,5-dimethyl-A3-

thiazoline (prepared according to Example 2) 3

Heliotropin 30

p-cresylphenylacetate 15

Oxyphenylon 1

p-cresol 2

Acetylisoeugenol 20

Isoeugenol 15

Ylang extra 5

Nerol 50

Geraniol 40

Terpinenol 4 5

a-terpinineol 35

Linalool (synthetic) 50

Benzyl alcohol 80

Benzyl acetate 10

p-cresyl salicylate 50

The 2- (2'-methylpropyl) -4,5-dimethyl-A3-thiazoline gave this preparation a deep green, coffee-like note that is so important for a narcissus perfume.

Example 19 Preparation of a soap composition 100 g of soap chips were mixed with 1 g of the compound according to Example 18 until an essentially homogeneous mass was formed. The scented soap had an excellent narcissus aroma with deep green and coffee-like nuances.

Example 20 Preparation of a Detergent 100 g of a detergent powder, prepared according to Example 1 of Can. PS 985 597, were mixed with 0.15 g of the perfume preparation according to Example 18 until an essentially homogeneous mass was formed. This composition had an excellent narcissus aroma with deep green and coffee-like nuances.

Example 21 Preparation of a Cosmetic Powder 100 g talcum powder was mixed with 0.25 g of the narcissus preparation according to Example 18 in a ball mill. The powder had an excellent narcissus aroma with additional deep green and coffee-like nuances.

Example 22 Perfumed Liquid Detergent Concentrated liquid detergents with a rich, pleasant narcissus aroma were formed, containing 0.10%, 0.15% and 0.20% of the narcissus preparation from Example 18. The detergents were all made with anionic agents and contained a 50:50 mixture of sodium lauroyl sarcosinate and potassium N-methyllauroyl tauride. All detergents had a pleasant fragrance that can be described as a narcissus with deep green and coffee-like nuances.

Example 23 Colognes and handkerchief perfume The preparation according to Example 18 was added to a colognes, namely in a concentration of 2.5% in 85% aqueous ethyl alcohol and to a handkerchief perfume in a concentration of 25% in 95% aqueous ethyl alcohol. This preparation gave the colognes and the handkerchief perfume a distinctive and certain strong narcissus scent, which also had intense and pleasant, hidden deep green and coffee-like nuances.

Example 24

Cologne water and handkerchief perfume 2-n-propyl-2,4,5-trimethyl-A3-thiazoline, prepared according to Example 4, was put into a Cologne water at a concentration of 2.5% in 85% aqueous ethyl alcohol, and in is a handkerchief perfume introduced in a concentration of 20% in 95% aqueous ethyl alcohol. Both the colognes and the handkerchief perfume received a distinctive and certain strong green, floral fragrance with tuberose and iris nuances.

20th

Example 25 Cologne water and handkerchief perfume 2- (2'-methylpropyl) -4,5-dimethyl-A3-thiazoline, prepared according to Example 2, was placed in a Cologne water in a concentration of 2.5% in 85% aqueous ethyl alcohol; and put into a handkerchief perfume at a concentration of 20% in 95% aqueous ethyl alcohol. Both the colognes and the handkerchief perfume were given a distinctive and certain strong 30 kalfee-like fragrance with excellent green nuances.

Example 26

Use of 2- (2'-methylthioethyl) -4,5-dimethyl-A3-thiazoline in tobacco 35 The following tobacco mixture (A) was produced:

Components parts

Ethyl butyrate 0.05

40 ethyl valerate 0.05

Maltol 2.00

Cocoa extract 26.00

Coffee extract 10.00

Ethanol (95% aqueous) 20.00

45 water 41.90

A second tobacco blend (B) was prepared as follows:

so components parts

Light tobacco 40.1

Burley tobacco 24.9

Maryland Tobacco 1.1

55 Turkish tobacco 11.6

stripped tobacco (hot-dried) 14.2

Glycerin 2.8

Water 5.3

6o The mixture (A) was added to a portion of the smoking tobacco mixture (B) in an amount of 0.1% by weight of the tobacco. The seasoned and unseasoned tobacco blends were then processed into cigarettes in a conventional manner.

65 Half of the cigarettes in each group were 100 T / Mill. the 2- (2'-methylthioethyl) -4,5-dimethyl-A3-thiazoline from Example 10 was added. It was found that the use of the thiazoline according to the invention in

13

630 512

Cigarettes were given a burnt aroma with a pleasant, slightly greasy nuance before smoking. These notes were also found in the smoked wort and the tobacco wort was more aromatic when smoked and made the tobacco "lighter", regardless of whether the other seasoning components of the mixture (A) were present or not.

Example 27

Use of 2- (2'-methyl-n-propyl) -4,5-dimethyl-A3-thiazoline in tobacco

The same mixtures (A) and (B) as in Fig. 26 were prepared.

The seasoning mixture (A) was added to part of the tobacco mixture (B) in an amount of 0.1% by weight of the tobacco. The seasoned and unseasoned tobacco blends were each made into cigarettes using conventional manufacturing methods.

Half of the cigarettes in each group were 2- (2'-methyl-n-propyl) -4,5-dimethyl-A3-thiazoline from Example 2 in an amount of 100 T / Mill. admitted.

The cigarettes seasoned with the thiazoline gave them a chocolate and nut-like, sweet aroma reminiscent of bread and baked goods and a similar taste before smoking. The same spice notes were found in the smoke and when smoked, these cigarettes had a sweeter, nutty and bread-like aroma with light green and light chocolate-like nuances, which brought them close to "light" tobacco, regardless of whether there were any other seasonings in the mixture (A) were present or not.

Example 28

Use of 2- (2'-n-butyl) -4,5-dimethyl-A3-thiazoline in tobacco

The same mixtures (A) and (B) as in Example 26 were prepared.

The seasoning mixture (A) was added to part of the smoking tobacco mixture (B) in an amount of 0.1% by weight of the tobacco. The seasoned and unseasoned tobacco blends were each made into cigarettes using conventional manufacturing methods.

Half of the cigarettes in each group were 2- (2'-n-butyl) -4,5-dimethyl-A3-thiazoline from Example 3 in an amount of 100 T / Mill. admitted.

The cigarettes seasoned with the thiazoline gave them a sweet, slightly green, nut-like, bread-like aroma and a similar spice character before smoking. The same notes were

5 If found and when smoking, the tobacco wort had a noticeably cooling character with light bread-like nuances that came very close to "light" tobacco, regardless of whether other seasoning components of the mixture (A) were present or not.

10th

Example 29 Tobacco Seasoning Mixture A tobacco seasoning mixture was prepared from the following components:

15

Components parts

Bergamot oil, Italy 5.00

Ylang-ylang oil 1.20 20 2- (2'-methyl-n-propyl) -4,5-dimethyl-

A3-thiazoline from Example 2 1.40

Acetophenone 1.20

Phenylacetaldehyde 0.50

Phenylethyl isovalerate 1.00

25 methylheptyl carbonate 0.50 3-phenyl-4-pentenaldiethylacetal, prepared according to that described in US Pat. No. 3,922,237

Procedure 10.00

95% aqueous ethyl alcohol 69.40

This seasoning mixture became smoking tobacco in amounts of 0.10% each; 0.20% and 0.30%, based on the weight of the dry tobacco, and then processed to save Ziga-35. The purpose of adding 3-phenyl-4-pentenaldiethylacetal is to give tobacco a hay-like, clove-like flavor with fruity notes when smoking. The 2- (2'-methyl-n-propyl) -4,5-dimethyl-A3-thiazoline acts as an excellent additive at a concentration of 200 T / Mill., Based on the dry weight of the tobacco to give the tobacco seasoning mixture a strong, intense, long-lasting «bright» note. This is due to the bread-like, nut flavor notes that are conferred by the thiazoline derivative.

Claims (7)

630512 2nd 1. Organoleptic modifier, characterized in that it contains at least one compound of the formula (1) as active component (1) contains, in which RA and Rc are identical or different and are hydrogen or methyl and RB is alkyl or alkylthioalkyl. 2. Process for the preparation of compounds of formula (1) (1) in which RA and Rc are the same or different and denote hydrogen or methyl and RB is alkyl or alkylthioalkyl, characterized by (1) reaction of a corresponding compound of the formula (4) R (4) O with ammonia to form a corresponding compound of formula (5) R, N \ (5) H HS 0 W / \ (6) means either an alkyl or an alkylthioalkyl group as organoleptic modifiers. 4. Modifier according to claim 1, characterized in that it as such a compound of formula (1) such s of formula (la) io (1a) 15 contains, in which one of the groups Rx, R2 and R3 are methyl and all other hydrogen atoms. 5. Modifier according to claim 1, characterized in that it is a compound of the formula (1) of the formula (Ib) 2a R12 : N 12 (1b) contains, in which Ru and Ri2 are the same or different and are hydrogen or methyl. 6. Use according to claim 3, characterized in that the compound of the formula (1) is one of the formula (Ia) R1 55 40 there) (2) reaction of the compound of formula (5) with a corresponding compound of formula (6) in which one of the groups R15 R2 and R3 is methyl and all the other hydrogen atoms. 7. Use according to claim 3, characterized in that the compound of the formula (1) is one of the formula (1b) 50 (1b) and (3) separating a composition from the reaction product which contains a predominant proportion of the compound of the formula (1). 3. Use of compounds of the formula (1) (1) in which RA and Rc are the same or different groups and are either hydrogen or the methyl group and RB is in which Rj j and R12 are the same or different and are hydrogen or methyl. 55