DE2503555A1 - METHOD FOR MODIFYING THE TASTE OF INGESTABLE SUBSTANCES - Google Patents

Description

v. April 18, 1974 in Great Britain Note No .: 17 088/74

The invention relates to the taste modification of food and luxury foods and other orally ingestible compositions / such as mouthwashes, dentifrices and chewing gum, i.e. compositions that can be put in the mouth. ingested but not necessarily swallowed and do not necessarily have nutritional value. The invention also relates to the taste modification of other tasty substances, such as tobacco.

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It is well known to the flavor technologist that very much small amounts of certain compounds, such as monosodium glutamate, have a significant effect on the taste of Compositions to which they are added have such an effect well above the change in taste which can be attributed to the taste of the additive itself. In fact, for the most part the amount of additive used is significantly below the Taste threshold of the compound used, and quite often the amount is as little as 1 or 2 ppm or even lower. Such additives are known in the art as "flavor enhancers" or "flavor enhancers" Known as "flavor condensing agents". The exact manner in which these compounds work is unknown. Some seem to work in such a way that they increase the perception of a certain taste, i.e. by "taste potentiation" in a narrow sense of this term, while others seem to act to the point of perception suppress unwanted taste components and thus allow other more desirable taste components to emerge. In the Throughout this specification, the term "taste modifier" is used in a broad sense to include any Change in taste brought about by the additive which cannot be ascribed to the taste of the additive itself is to include, the latter either due to the fact that the additive is tasteless or that of very little concentration is used to him.

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Other compounds known as face modifiers are and are used are, for example, 5'-nucleotides, such as disodium 5'-inosinate and disodium 5'-guanylate, Cyclamic acid, Ν, Ν'-di-o-tolylethylenediamine, dioctyl sodium sulfosuccinate and 3-hydroxy-2-methyl-4-pyrone (maltol). See, for example, Handbook of Food Additives, 2nd edition (1972), CRC Press, pages 513 to 521, Flavor Chemistry (1966), American Chemical Society, pages 261 to 273, Flavor Research, Edited by Teranishi, Hornstein, Issenberg and Wick, published by Academic Press, pages 5 to 12.

The exact mode of action of these known facial skin modifiers is not fully explainable. A number of studies regarding the influence of different non-interrelated related compounds on the taste receptors in humans, such as acetylcholine and menthol, was made, see Skouby A.P. and Zilstorff-Pedersen, Acta Physiologica Scand. (1955), 34, pages 251 to 258 and Hellekant G., Acta Physiologica Scand. (1969), 76, pp 361 to 368. However, no attempt has been published to date a general structure with either an awareness or desensitization of the taste receptors Humans or interact with the presence or absence of taste-modifying activity bring.

In a somewhat different area of physiological activity, a select number of compounds have recently been used with. "

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physiological cooling activity on the body's nervous system, similar to that obtained with menthol, found. Such connections are described, for example, in the following DT-OS: 22 02 535.O, 22 02 255.7,

22 O3 273.1, 22 03 947.0, 23 16 999.5, 23 17 000.5, .23 17 538.4, 23 17 539.4, 23 34 985.1, 23 36 495.6,

23 45 156.1, 24 13 639.8, 24 39 770.4.

Although, as stated above, a number of compounds has already been used extensively in the food industry as a taste modifier is the number still relatively small, and there is a need for additional compounds that are active as taste modifiers are, especially of compounds that can be easily synthesized, partly to those of the flavor technologist to increase the available choice, partly also to avoid disadvantages. to overcome known connections, for example in the case of of monosodium glutamate / the requirement to be a relative

undesirable in large quantities with the associated risk Use side effects. There is also a need for taste modifiers in specific areas such as for example, to lessen the bitter aftertaste of some artificial sweeteners or the relatively bad one To improve the taste of valuable protein foods of natural, synthetic or semi-synthetic origin or modify it.

The object underlying the invention is now to meet this need, and is based on the fixed

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position that, generally speaking. Compounds with a physiological cooling activity, as described for example in the DT-OS mentioned above, also have a taste-modifying activity when they are added to flavor-containing ingestible preparations or substances, including tobacco, in amounts below those that are required in order to achieve a noticeable stimulation of the cold receptors of the nervous system in the mucous membranes of the mouth and / or the gastrointestinal canal _r when the preparations are ingested or, in the case of tobacco, smoked.

According to the invention there is therefore a method of modification the taste of ingestible substances or preparations containing taste, including tobacco, and this method consists in adding a compound other than menthol to the preparation containing the taste, which can stimulate the cold receptors of the body's nervous system, incorporated in an amount below that Threshold value of practical physiological cooling activity, as defined below, lies.

According to the invention you also get ingestible preparations, including tobacco which is a flavoring agent and a taste modifier contain, which is a compound other than menthol with the ability of the

Stimulation of the cold receptors of the body's nervous system is and in an amount below the threshold

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practical physiological cooling activity is included.

Broadly speaking, the compounds useful as taste modifiers in the invention, i.e., compounds having the ability to stimulate the cold receptors of the body's nervous system when in contact with them with the formation of a cooling sensation, can be represented by the following formulas:

J *

R ₂ -OX > ^π E ₅ -P = O _and

wherein in formula I:

R. means H or C.-a.-alkyl, 1 Xb

R ₂ and "R taken separately each denote alkyl groups or cycloalkyl groups with up to 6 carbon atoms or else with up to 7 carbon atoms, if X _{denotes OH or CH 2} OH,

R_ and R- taken together are straight-chain or branched-chain C.-C., - denote alkylene group, where

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i) when R 1 denotes a hydrogen atom, the alkylene chain is branched on a carbon atom in a ß- or jt -position with respect to the group X,

ii) when X is OH or CH ₃ OH, the alkylene group can also contain an OH substituent, and '-

iii) when R, is a hydrogen atom and X is OH, the cyclic group of the general

Formula __ _{CH R}

L? . I - ■

no p-menth-3-yl group means

R ,, R- and R- together a total of 6 to 18 carbon ~ possess atoms and

X OH, CH-OH, C00R ", CONR-R _n , SONR-R- or e. ι ο y Χ · ο y

SO R, _Q means where.

R_ is a hydrogen atom, an alkali or alkaline earth metal, an ammonium or alkyl or hydroxyalkyl substituted ammonium group or a hydroxyalkoxyalkyl group, Hydroxyalkyl group, carboxyalkyl group or alkylcarboxyalkyl group with up to 12 carbon atoms means,

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R ₀ and R _{n taken} separately are each hydrogen atoms ο y

or alkyl groups, hydroxyalkyl groups, carboxyalkyl groups or alkylcarboxyalkyl groups with up to carbon atoms, where, when R _{0 is} H, Rq is also a cycloalkyl group with up to 8 carbon atoms. substance atoms, a phenyl radical or benzyl radical or substituted phenyl or benzyl radical with hydroxyl, amino, C, -C - alkyl or C ^ -C. -alkoxy substituents or

R ₀ and R _{n taken} together represent an alkylene group with up to 12 carbon atoms, where the carbon atom chain can optionally also be interrupted by oxygen or an -NH group,

R, q is an alkyl, hydroxyalkyl, carboxyalkyl or Is an alkylcarboxyalkyl group with up to 12 carbon atoms and

χ is 1 or 2

and where in formula II

R. denotes a C ₃ -C ₂₀ -alkyl group,

Rr is a C - Cg-alkyl or cycloalkyl group,

R- denotes a C, -Cg-alkyl group or C_-Cg-cycloalkyl group, where at least one of the groups R ₄ , R ₅

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- Q _

and Rg is branched on the carbon atom in a ⁰ ^ -, ß- or δ -position with respect to the phosphorus atom, and

R ₄ , R ₅ and Rg together have a total of 10 to 24 carbon atoms,

and where in formula III *

^R 1T 9, taken ^{separately, denotes} H, a C - ^ - Cg-alkyl group or a C ₃ -Cg -cycloalkyl group,

^R 12 9, taken ^{separately, denotes} a C ₃ -C, ₀ -alkyl group or C 1 -C 4 alkylcycloalkyl group, a cycloalky group or cycloalkylalkyl group, where R ^ _{2 is} branched on a <λ- or ß-carbon atom with respect to the nitrogen atom is if, in the case of cyclic groups, the carbon atom is in the ⁰ ^ - or ß-position to the nitrogen fatom part of the ring,

^R ll ^{un (} ^ ^R 12 ^{together enoinmei: 1 denotes} a branched-chain alkylene * group with 3 to 7 carbon atoms and with a branch on the <A or ß carbon atom with respect to the nitrogen atom, the chain optionally being an ether (0) - Contains oxygen atom,

^R ll ^R 12 ^un ^ 9 ^etrennt taken or taken together contain the total at least 5 carbon atoms and

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YR ₁₃ CO-, R ₁₄ SO ₂ - or R ₁₅ R _{ß is} NCO,

wherein
. R ₁₃ H, a C ₁ -Cg alkyl group or alkenyl group, a C ^ -Cg cycloalkyl group, a C, -C- hydroxyalkyl group, • a C ^ C ^ -carboxyalkyl group, a C ₃ -C ₁ -alkylcarboxyalkyl group, denotes a phenyl radical or a C, -C ₄ -alkyl groups, C, -C ₄ -alkoxy groups, OH, COOH or NO2 as substituents, where, when R ₁₃ denotes a Cg-alkyl group, has this primary structure,

R is a C - ^ - Cg-alkyl group or C ₃ -Cg -cycloalkyl group, where, if R _{14 is} a C ₁ - or 'C _fi -alkyl group, this has a primary structure,

and R ₁₆ taken separately are each H, C "-CG alkyl, C_ ~ Cg-AlkyIcycloalkylgruppen, cycloalkyl or cycloalkylalkyl, C, -. C ₁₀ hydroxyalkyl groups / C ₃ -C, ₀ ~ carboxyalkyl or ^C 3 ~ ^c ~ iq Alkylcarboxyalkylgruppen denote or together denote a straight-chain or branched-chain C -, - C, _o -alkylene group which is optionally substituted by oxygen or an oxygen-containing group or contains an ether oxygen atom, and

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25O3S55 ' ^u "

,, / R _ and Υ together a total of 7 to 16 carbon contain atoms.

It has already been said that the taste modifiers used according to the invention contain compounds with a physiological cooling effect on the body. That is, when in contact with the cold receptors of the nervous system are brought about, they cause a physiological reaction, which as a feeling of cooling in the area of the body, to which the compound was applied is perceived. However, the compounds are used in the present invention in amounts which are below those which are necessary to produce a noticeable cooling effect in the mouth when the flavored preparations or substances are ingested, such amounts being defined here as being below the threshold value of practical physiological cooling activity.

According to the present invention as a taste modifier Compounds used in the medium differ largely in their cooling activity, i.e. the amount required to producing a noticeable cooling effect when the compound is applied to the body is very different. aside from that can also perceive the cooling effect affects other components of the flavored preparation and sensitivity to these compounds will vary from person to person. thats why it is not possible to provide any absolute value for the required

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borrowed amount of a compound for the production of a noticeable cooling effect in the mouth when ingesting the flavoring-containing preparations. For the However, the present invention becomes the threshold of practical physiological cooling activity of a given one Compound in a given preparation determined by the following test procedure:

Since _f, as stated above, the sensitivity to the cooling activity of the compounds used according to the invention varies not only from compound to compound and from preparation to preparation, but also from test person to test person, testing must be carried out on a statistical basis. Tests of this type are commonly used in testing the organoleptic properties, ie taste, smell, etc., of organic and inorganic compounds, see Kirk-Othmer, Encyclopedia of Chemical Technology, S. Edition (1967), Volume 14, pages 336-344.

In the test procedure described below, the tests are carried out with a selected group of six people average oral sensitivity to 1-menthol carried out.

To select this test group of average sensitivity, v / ground known amounts of 1-menthol, dissolved in petroleum ether (bp 40 to 60 C) on 5 mm long squares of Filter paper, after which the solvent evaporates

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will / so that the squares with known amounts of 1-menthol remain impregnated. A group of test persons * is asked to stand on an impregnated square for a while to put the tongue and report whether a feeling of coolness is detected or not. The amount of 1-menthol up each impregnated square is gradually changed by one Value significantly above 0.25 .ug / square to significantly below 0.25 / Ug, the exact range being unimportant is. It is convenient to start with squares, the 2/0 / Ug 1-menthol, the amount of each subsequent square being half that of the preceding square i.e. the second test square contains "1.0 / Ug, the third O, 5 / Ug etc. Any amount is on the tongue at least 10 times tested. In this way, the thresholds for cold formula stimulation by 1-menthol "become" for each individual of the group, the threshold for each individual being the amount of 1-menthoi at which a cooling effect is reported 50% of the time in a series of no less than ten test applications. Six people of the group are now selected whose threshold value for 1-menthol is in the range from 0.1 μg to 10 μg and their average threshold is about 0.25 µg. This selected group is now called the test group considered average sensitivity.

To reach the threshold practical physiological activity of compounds used as taste modifiers according to of the invention are used to obtain the

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six selected people of the test group asked to taste samples of the flavored preparation with increasing To test amounts of the taste modifier for taste, tasting each sample at least 10 times and to report whether or not there is a cooling effect in the mouth. The threshold more practical physiological Cooling effect for a specific compound in a specific preparation is then considered to be for each person in the group recorded the amount at which a cooling effect is reported 50% of the time, i.e. in the case of each sample 10 times In this case, the cooling effect must be checked for taste at least in five cases by each person perceived by the group. The individual values obtained in this way are then averaged and give the average Threshold of practical cooling activity for the whole group.

Although this method has the upper limit of the amount of the taste modifier which can be used in accordance with the invention also become taste-modifying Effects obtained when modifier amounts are significantly below the threshold value for physiological cooling activity be used. Generally speaking, the amount of modifier used is from 0.01 to 100 ppm (parts per million) of the flavored preparation based on how it is consumed, i.e. how it is ingested will. Concentrates, such as fruit juice concentrates, which should be diluted before use, contain larger quantities of the flavor modifiers, so that one

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thin to the modifier concentration in the specified Area is coming. The amount of modifier used actually varies widely from compound to compound and from preparation to preparation, but amounts in the above range are generally satisfactory and amounts in the range ranging from 0.1 to 10 ppm are generally preferred. According to the invention it was also found that in general with with increasing concentration of the modifier up to a certain maximum, an increase in the taste-modifying activity occurs, but above the maximum the taste-modifying effects become less noticeable. So there is an optimal one for each particular connection Concentration range to obtain maximum flavor modification, this range from compound to compound and also varies from composition to composition, and above and below this range the taste-modifying effects are reduced. Because of the individual variations, no generally applicable Limits can be given for the optimal concentration range, yet one can easily define these limits for a particular one Compound in a certain composition on the basis of a series of routine experiments similar to those that described above.

The test procedure described above can also be used to test compounds with physiological activity that are known to be Taste modifiers of the invention are useful to identify and define. Connections with a

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physiological cooling activity necessary for the present Invention useful can be defined as those compounds that when tested against a selected Group according to the method used to select the group / i.e. when placing squares of filter paper, which is impregnated with increasing amounts of the compound has an actual threshold activity of 100 µg or own less.

It should be noted, therefore, that the term "threshold value for practical physiological cooling activity ¹¹ as used herein relates to the activity of the compounds when incorporated into the ingestible preparation, while the term" actual threshold value for physiological cooling activity "relates to the activity of the compounds when applied essentially directly to the tongue with an inert tasteless medium, ie, in the filter paper square.

In a practical demonstration of the above The test procedure was for six people with individual thresholds for 1-menthol ranging from 0.1 to 10.0 µg and an average threshold value of about 0.25 / Ug according to the method described.

This group of six people was then used in an initial test to make the actual threshold more physiological Cooling activity of the two specified compounds

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to investigate. In this test, each subject was asked to filter paper squares, each marked with a Amount of the designated compound were impregnated, to be placed on the tongue according to the procedure described above and report whether or not there was a cooling effect. The responses of each subject were recorded, and the lowest amount that answers positive in at least- 50% of the cases where that amount is tested was found to be taken as the actual threshold. The individual threshold values were then averaged and gave the average value for the group.

The six subjects were then used in a second test to determine the threshold practical physiological cooling activity of the two compounds in an aqueous orange beverage. For this purpose, the six test subjects were asked to taste a series of samples of 25 ml each of a commercial orange juice diluted with water and 2, 4, 6, 8, 10 and 12 g / ml (ie ppm) the both selected compounds. The samples were administered in a random order with a 5 minute interval between each sample. Each test person was asked to report whether or not there was a cooling effect in the mouth. In this part of the procedure, each sample was only seasoned once to shorten the duration of the test. A preliminary value for the threshold value of physiological "cooling activity" of each compound was thus obtained for each individual test person.

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_ 1 Q _

IO

Fresh dilute orange juice solutions were then made up and in three separate 25 ml portions of each solution for each subject, amounts of test compound were added just above, just below, and equal to, respectively, the preliminary threshold of the first part of the procedure obtained above. Each of the three portions of 25 ml each was then administered to the respective test person in order to taste a total of ten individual samples at 5-minute intervals and in any order. Again, the subject was asked to report whether or not there was a cooling effect, and the smallest amount of the compound _r that gave positive responses in at least five out of ten cases was taken as the threshold of practical physiological cooling activity. These individual values were then averaged for the whole group.

The results obtained were as follows:

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Connection A

Connection B

Test- threshold- actual- practi- actual- practi-

person worth shear licher shear -

No. compared to threshold threshold threshold threshold threshold

Menthol, worth, worth, worth, worth

, ug aig in orange i orange

¹ ' drink, / ⁹ drink,

/ Ug / ml, ug / ml

1 0.3 0.3 8th 1.0 8th 2 0.1 0.05 7th 0.3 2 3 0.3 0.3 6th 2.0 8th 4th 0.3 0.1 6th 2.0 8th 5 0.2 0.5 2 3.0 4th 6th 0.4 0.5 IO 3.0 12th middle value 0.27 0.29 5.5 1.9 7th

Compound A = N-ethyl-p-menthan-S-carboxamide Compound B = 2-hydroxyethyl-p-menthane-3-carboxylate "

In another test, the same six subjects were asked the taste of the same orange drink with a content of compounds A and B below the average threshold more practical physiological Cooling activity / that is stated above, to determine and. to report about it and taste · with that one Compare control sample that did not contain any additive. The following reports were obtained:

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link

Lot,
, µg / ml (ppm)

Flavor modification

0.2 0.8

0.2 0.8

1.5

increased sweetness and increased overall taste

increased sweetness, but little effect on the overall taste

increased sweetness, dry aftertaste,

increased sweetness and increased orange flavor, dry feeling in the mouth

very little effect, slightly dry feeling in the mouth

These results demonstrate the taste-modifying effects of the compounds of the invention when they be used in edible preparations in amounts below that required to be detectable To produce a cooling effect. They also show the decrease in taste-modifying activity above one certain concentration occurs.

The compounds used as taste modifiers according to the invention can be used in a wide range Flavored ingestible preparations can be used, such as in a wide range of foods and beverages Beverages and in a wide range of other flavored ingestible preparations, such as in U.S. Pat

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Orally administered medicinal products containing flavoring Oral hygiene preparations and preparations. Typi ^ see ingestible compositions into which they can be incorporated are flavored foods, such as chocolate, chocolate pudding and other mixed pudding types, jellies, canned goods, confectionery, bread, Starch foods, meat products, beverages such as coffee, tea, cocoa, drinking chocolate, non-alcoholic beverages, juices, Cola, beer and other alcoholic beverages, chewing gum * flavored mouthwashes, toothpastes, throat lozenges, orally administered drugs, etc. In many cases, the low volatility recommends those used in the invention Flavor modifiers their use in cooked foods that they are used during manufacture and before can be added to cooking.

Besides direct familiarization with food and enjoyment— medium, the taste modifiers according to the invention can also be used in flavoring additives, such as spices, Flavor essences, etc., are incorporated, which are even added in the production of food or used.

Mixtures of two or more compounds can also be used in accordance with the invention, as can mixtures the taste modifier according to the invention with known ones Taste neutralizers, such as monosodium glutamate.

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As already indicated, the taste modifiers used according to the invention can also be used as taste modifiers used in tobacco and preparations containing tobacco, v / ie cigarettes, cigars, pipe tobacco and chewing tobacco will.

The taste modifiers used in the invention can be in the ingestible supplements at any time during preparation or immediately before ingestion can be incorporated, such as as a condiment or sweetener. They can be volatile as such or in an appropriate or solid carriers can be added to aid dispersion.

The compounds used as taste modifiers in the present invention are discussed in detail below.

cyclic amides

Among the most useful compounds used as taste modifiers are used according to the invention, there are cyclic amides of the general formula IV

(CH ₂ ) _n

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where η is O or an integer from 1 to 6, R is a C, -C ₅ ~ alkyl group,

y is an integer from 1 to 4, at least one group R in a 1-, 2- or 3-position in the ring is located

R ₂₃ , taken separately, denotes a hydrogen atom or an alkyl or hydroxyalkyl group with up to 12 carbon atoms,

^R 29 9, taken ^{separately, denotes} a hydrogen atom, an alkyl group, a hydroxyalkyl group, a carboxyalkyl group or an alkylcarboxyalkyl group with up to 12 carbon atoms, where, if R ₂ g is H, R _{39 is} also a cycloalkyl group with up to 8 carbon atoms, a phenyl group, a benzyl group or substituted phenyl or benzyl radical with hydroxyl groups, CjC ^ -alkyl groups or C.-C ^ -alkoxy groups as substituents and a maximum of 12 carbon atoms or

R ₃₈ and R _{29 taken} together represent an alkylene group with up to 12 carbon atoms, which optionally also contains an oxygen heteroatom.

These amides can be reacted in a conventional manner of the corresponding acid chloride with a suitable amine.

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Many of the cyclic amides (and other compounds that used as flavor modifiers according to the invention) exhibit either geometric or optical isomerism or both, and depending on the starting materials and methods used in their preparation, the compounds be isomerically pure, i.e. consist of a geometric or optical isomer, or they can be mixtures of isomers, and in a geometrical as well as in an optical sense. Generally, the compounds are used as a mixture of isomers, however In some cases, the taste-modifying effect can differ between geometric or optical isomers, see above that one or the other isomer may be preferred.

Amides of formula IV with a secondary alkyl group, such as an isopropyl group or sec-butyl group in a 1- or The 2-position of the ring are of particular interest as taste modifiers according to the invention, with p-menthane ~ 3-carboxamides of the formula V being particularly preferred:

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wherein R ₂ g and R _{29 have} the above meaning.

Another group of cyclic amides of particular interest are cycloheptane carboxamides and cyclooctane carboxamides of general formula VI

wherein m is 2 or 3, at least one of the groups
R ₂ -J and R ₂ - a C, -Cj - alkyl group _r especially a secondary alkyl group, and the other is a hydrogen atom or a CjC, - alkyl group and R ₂ g and R ₂ ^ have the above meaning.

Generally speaking, preferred amides are those wherein
R _{28 is} hydrogen and R _{2 is} Q. Is hydrogen atom, a C1 -C4 hydroxyalkyl group, alkylcarboxyalky group with up to 6 carbon atoms, C1 -C6 cycloalkyl group, a phenyl radical or a phenyl radical substituted by hydroxy, methyl or methoxy substituents, and in addition are
preferred compounds also include disubstituted amides in which R ₂₈ and R _{29 are} each C 1 -C 4 alkyl groups or C 1 -C 6 hydroxyalkyl groups.

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Typical compounds according to Formula IV, which are used as taste modifiers are useful according to the invention are listed in Table I below.

Table I.

N-ethyl-1-isopropylcycloheptane carboxamide Njl-diisopropyl ^ -methylcyclopentanecarboxamide

K- (I ¹ , 1'-diraethyl-2-hydroxyethyl) -1-sec-butylcycloheptane carboxamide

^ !, N-Dimethyl-l-ethylcyclooctanecarboxamide N- (2'-Isopropylcycloheptanecarbonyl) -glycine ethyl ester N- (I ¹ -ethyl-2'-methylcycloheptanecarbonyl) -morpholine Np-methoxyphenyl-lO-ethyl-2-methylcycloheptane-2-methylcycloheptane 1-sec-butylcyclohexanecarboxamide Nn-butyl-ln-propylcyclohexanecarboxamide N-ethyl-2,5-dimethylcyclohexanecarboxamide N, N, 2,3 / e-pentamethylcyclohexanecarboxamide

N- (2'-hydroxyethyl) -l-ethyl-S-methyl-G-isopropylhexanecarboxamide

N, N, 2,3, -Tetramethy1-1-ethylcyclohexanecarboxamide 1-ethyl-2-isopropyl-2-methylcyclohexanecarboxaInide p-menthane-3-carboxamide

N-ethyl-p-menthane-3-carboxamide N- (p-menth-3-oyl) -glycine

N-Benzyl-p-menthane-3-carboxamide, N-p-hydroxyphenyl-p-menthane-3-carboxamide N-isopropyl-p-menthane-3-carboxamide K- (6'-hydroxy-n-hexyl) -p-menthane-3-carboxamide

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N- (p-menth-3-oyl) -morpholine N-methyl-N- (p-menth-3-oyl) -glycine ethyl ester N- (p-Tolyl) -p-inenthan-3-carboxainide

N- (1 ·, I ¹ -dimethyl-2'-hydroxyethyl) -1,2-diethylcyclohexanecarboxamide

H- (1 ', 1' -Dimethyl-2 '-hydroxyethyl) -p-iaenthan-3-carboxainide N-tert-butyl-p-menthane-3-carboxamide ■ N- (p-menth-3-oyl) -glycine-n-propyl ester N-ethyl-1-isopropylcyclohexane carboxamide N-Cyclopentyl-1-isopropylcycloheptane carboxamide N-n-octyl-1-isopropylcycloheptane carboxamide N-methyl-1-ethylcyclo-undecancarboxamide N- (1 * -ethyl-2'-methylcycloheptane carbonyl) -pyrrolidine N- (p-menth-3-oyl) -glycine-n-propyl ester

N / N-dimethyl-p-menthane-S-carboxamide -

N- (carboxymethyl) -p-menthane-3-carboxanide N- (p-menth-3-oyl) -piperidine N- (p-menth-3-oyl) -piperazine N- (p-methoxyphenyl) -p-inenthan-3-carboxamide N-n-decyl-p-menthane-S-carboxamide N-cyclopropyl-p-menthane-S-carboxamide N-Cycloheptyl-p-menthane-S-carboxamide N-Cycloheptylmethyl-p-menthane-S-carboxamide

Ν, Ν-d ¹ , 4 '-Dimethyl-S'-'- äth.yltetramethylene) -p-menthan-3-carboxamide ■

N- (3 '-Hydroxy-4' -methylphenyl) -p-inenthan-3-carboxamide N-phenyl-p-menthane-3-carboxainide N- (2'-n-Butylcyclohexanecarbonyl) glycine ethyl ester N- (I'-n-propylcyclohexanecarbonyl) -niorpholine

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N- (5'-Hydroxy-n -pentyl) -1-isopropyl-2-methylcyclopentanecarboxamide

N-ethyl-1-isopentylcyclopentanecarboxamide N- (1 '^ isopropylcyc'lopentanecarbonyl) glycine ethyl ester N, 1,4,4-tetramethylcycloheptane carboxamide

N- {3'-4'-dimethylphenyl) -1-isopropylcycloheptane carboxamide

N- (3 ', 3', 7 '-trimethylcycloheptanecarbonyl) -glycine ethyl ester N-methyl-2-ethylcycloheptane carboxamide

N- (1 ', 1'-dimethyl-2-hydroxyethyl) -1-ethylcyclooctane carboxamide

N, 2-diethylcyclooctane carboxamide

N- (1 ', 1'-dimethyl-2'-hydroxyethyl) -l-ethylcyclo-undecancarboxamide

N ^ N-dimethyl-1-ethylcyclo-undecancarboxamide

Numerous other cyclic amides with physiological cooling activity, those according to the invention as taste modifiers are useful, are described in DT-OS 22 03 535, 22 02 255, 23 17 539, 24 13 639 and 24 58 562, and the contents of all of these DT-OS are incorporated into the present disclosure.

acyclic secondary and tertiary amides

A second group of amides useful in accordance with the invention are acyclic secondary and tertiary amides of the general type Formula VII

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250355 YII

wherein R _{1 is} H or C ₁ -C ₅ -Al] CyI, R "and R are each C ₃ -C 4 -alkyl groups, Rw R" and R ₃ together contain a total of 5 to 15 carbon atoms and.

R ^ o and R "n are as defined above.

Acyclic amides of formula VII with physiological cooling activity and usefulness as taste modifiers according to the invention are "described in detail in DT-OS 23 17 538, to which reference is made here. Generally speaking, they can be obtained by conventional methods of making amides, such as for example by reacting the appropriate acid chloride with ammonia or a suitable amine.

Preferred acyclic amides of formula VII for use as taste modifiers are those in which at least one of the groups R 1, R 1, and R- is a branched chain alkyl group, preferably having a branch in a ^ - or beta-position with respect to the carbon atom which the group CONR ₂₈ R ₂ Q is attached. Preferred values for R ₃₈ and R ₃₉ are listed above for the cyclic amides.

- 3o -

50 98 33/0598

Typical acyclic amides of the formula VII are listed below in Table II.

Table II '

N ₁ N, 2-triethyl-3-methylpentanamide N, 2> 3, -trimethyl-2-isopropylbutanamide N-ethyl-2,3-dimethyl-2-isopropylbutanamide N, 2,2-triethyl-3-methylbutanamide N- { 2 ~ isopropyl-2, 3-dimethylbutanoyl) -glycinäthylester N _/ N-2-trimethyl-2-isopropylhexanamide 2,3-dimethyl-2-sec-butylpentanaraid _{(2/4-dimethyl-2-isobutylpentanoyl)} piperidine N, 2 -diisopropyl-3-methyIbutanamid N-ethyl-2, 4-dimethy1-2-isopropylpentanamid N, 2-diethyl-5-methylhexanamide N, 2-Di-sec-butyl-3-methyl pentanamide N-ethyl-2-isobutyl-4 -methylpentanamide N-ethyl-2,3-dimethyl-2-sec-butylpentanamide N- (I ¹ , l ^l -dimethyl-2'-hydroxyethyl) -2,2-diethyIbutanamid N -ethyl-2,4-dimethyl-2 -isobutylpentanamide N _/ N _/ 2,2,4-Penta * -methylpentanamid N- (2'-Isobuty1-3'-methylbutanoyI) -glycine ethyl ester N, N, 3-trimethy1-2-ethylpentanamide N-Äthy1-2-isopropy1- 4-methylpentanamide N, N, 3-trimethyl 1-2-ethyibutanamide

-31--

509833/0596

cyclic carboxylic acids, their salts and esters

Of substantial interest as a taste modifier according to the invention are also secondary and ocular eye tertiary carboxylic acids, salts thereof and esters of the formula VIII

YHI

wherein n, y, R and R_ are as defined above.

The cyclic acids of Formula VIII can be obtained by conventional methods for the preparation of carboxylic acids and these can then easily be converted into their alkali, alkaline earth, ammonium, alkylamine and alkanolamine salts and their corresponding hydroxyalkyl esters. Preferred cyclic carboxylic acids, esters and salts are p-menthane-3-carboxylic acid and its derivatives according to the formula IX ^-

IX

I I

COOH ₇

wherein R is as defined above and is preferably a hydrogen atom or a C ₂ -C ₅ -hydroxyalkyl group.

- 32 -

5 0983 3/0596

25Q3555

Cycloheptane and cyclooctane carboxylic acids are also of particular interest of formula X

COOiI ₇

wherein m, R ₂ 3> ^R 24 ^{and R} 7 are ^as defined above.

Typical compounds of Formula VIII are listed below in Table III.

Table III

p-menthane-3-carboxylic acid

Triethylammonium p-menthane-3-carboxylate Sodium p-menthane-3-carboxylate

Ammonium p-menthane-3-carboxylate

Hydroxyethylaminonium p-menthane-3-carboxylate 2-hydroxyethyl-p-menthane-3-carboxylate 1-sec-butylcycloheptane carboxylic acid

2-isopropylcycloheptane carboxylic acid

1-Isopropy1-2-methy1eyeloheptane carboxylic acid 1 — ethyl cyclooctane carboxylic acid

2 ', 3'-dihydroxy-n-propyl-p-menthane-S-carboxylate 2 "- (2'-hydroxyethoxy) -ethyl-p-raenthan-3-carboxylate 1'-carboxy-1'-methylethyl-p- menthane-3-carboxylate I ¹ -ethoxycarbonylethyl-p-menthane-3-carboxylate

- 33 -

509833/05 9 6

1-isopropyl-2-methylcyclopentanecarboxylic acid 2-ethylcyclooctanecarboxylic acid

2'-hydroxyethyl-1-isopropyl-cycloheptane carboxylate 2 · -Hydroxyethyl-1-isopropy1-2-methylcyclopentanecarboxylate 2 * -hydroxyethyl-2-ethylcyclooctane carboxylate 1 '-Methyl-2' -hydroxypropyl-p-menthane-S-carboxylate l-sec-butylcycloheptane carboxylic acid 2-isopropylcycloheptane carboxylic acid 1-ethyl-2-methylcycloheptane carboxylic acid 1,4,4-rtrimethylcycloheptane carboxylic acid l-ethylcyclooctanecarboxylic acid

1-isopentyl-2-methylcyclopentanecarboxylic acid 2 · -Hydroxy-n-propyl-1-isopentylcyclopentanecarboxylafc 2'-hydroxyethyl-1-isopyl-2-methylcyclopentanecarboxylafc 2 * -Hydroxyethyl-1-ethyl-2-methylcycloheptane carbqxylate

Other cyclic carboxylic acids, salts and esters thereof with physiological cooling activity and usefulness according to the invention are listed in DT-OS 22 02 535 and 24 58 562, to which reference has already been made,

cyclic sulfonamides and sulfinamides

Cyclic sulfinamides and sulfonamides in general also have taste-modifying properties according to the invention Formula XI

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509833/0596

.y

SO W oftSOQ X 28 29

wherein R, y, R ₂ "χ!. or 2 is.

and

have the above meaning and

These cyclic sulfonamides and sulfinamides are in the DT-OS 23 36 945 described, to which reference is made here will.

The sulfonamides and sulfonamides can easily be converted by reaction of the corresponding acid chlorides with ammonia or with the appropriate mono- or disubstituted amine.

Preferred sulfonamides and sulfinamides for use according to the invention are p-menthane-3-sulfinamides and sulfone amides of the general formula XII

XIX

where x, R “q and R ~ g are as defined above. Preferably, R "o ^ur * d R59 are each hydrogen atoms or C -.- C; 2 ~ alkyl groups or hydroxyalkyl groups, namely such that R "o and R ~" together not more than 12 carbon

own atoms.

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509833/0596

250355S -35-

Typical cyclic sulfonamides and sulfonamides, which after, of the invention are shown in Table IV. Others are described in DT-OS 23 36 495, to which reference is made here.

Table IV

N- (2-hydroxyethyl) -p-menthan-3-sulfinamide M- (p-menthane-3-sulfonyl) morpholine K-Ethy1-2, S-dimethylcyclohexanesulfonamide N- (2 ·, 5'-dimethylcyclohexane-sulfonyl) -glycine ethyl ester N-n-Butyl-2-methylcyclohexanesulfinamide N, N-Dimeth.yl-p-menthane-3-sulfonamide K, N-diethyl-1-methylcyclohexanesulfinamide N-n-Butyl-p-menthane-3-rsulfynamide p-menthane-3-sulfonamide

N-ethyl-2, S-dimethylcyclohexanesulfinamide N-n-hexyl-1-methylcyclohexanesulfinamide N-n-Butyl-3-methylcyclohexanesulfonamide

acyclic sulfonamides and sulfonamides

Other sulfonamides and sulfinamides made according to the invention Acyclic sulfinamides and sulfonamides of the formula XIII are useful

XIH

. - 36 -

509833/0596

Therein R., R ₃ , R_, R ₃₈ and R are as defined above in connection with formula VII / and χ denotes 1 or 2.

Such connections are ben described in DT-OS 23 36 495.6.

Again, the acyclic compounds can easily be prepared from the appropriate acid chloride and ammonia or substituted amine. Preferred acyclic sulfonamides and sulfinamides for use according to the invention are those compounds according to formula XIII in which R ,, R ~ and R_ together have a total of 6 to 11 carbon atoms and R_g and R «Q are the preferred ones given above for the cyclic sulfonamides and sulfinamides Have values.

Typical acyclic sulfonamides and sulfinamides of the formula XIII are listed in Table V below.

Table V-

N, N-Diethyl-3-methylpent-3-ylsulfinamide, N-n-Octylpent-3-ylsulfinamide

N- (2'-hydroxyethyl) -N-methyl-2,8-dimethylnon-5-ylsulfinamide N-n-Hexyl-3-methylpent-3-ylsulfinamide N, N-Diisopropyl-2-methylpent-4-ylsulfinamide N-isopropyl-hex-3-ylsulfinamide.

N, N-diethy1-3-methylpent-3-ylsulfonamide N- (2-Methylhept-4-ylsulfinyl) piperidine

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509833/0596

Kn-hexyl-2-methylpent-3-ylsulfonamide N _/ N-dimethyl-2-methyloct-3-ylsulfinamide K- (2 »methyIoet-3-yl) -sulfinylmorpholine Nn-octylhex-3-ylsulfonamide

Other suitable compounds of the formula XIII are described in DT-OS 23 36 495, to which reference is made here will.

cyclic and acyclic sulfoxides and sulfones.

Other compounds with taste modifying properties according to the invention are cyclic sulfoxides and sulfones of the general formula XIV

XIT

¹ V

wherein R, x, y and R. _{Q are} as defined above, as well as

acyclic sulfoxides and sulfones of the general formula XV

wherein R, R ₃ and R are as defined above in connection with formula VII and R, _Q and χ are as defined in connection with formula I.

- 38 -

509833/0 5 96

~ 38

The cyclic and acyclic compounds according to the formulas XIV and XV with physiological cooling activity and Usefulness as a taste modifier according to the invention are described in detail in DT-OS 23 34 985. You can by oxidation of the corresponding sulfide getting produced.

Preferred cyclic sulfoxides and sulfones are of the formula-XIV, wherein χ is 1 or 2 and R is a C.-C ₁ --Alkylgruppe or hydroxyalkyl group or a Alkylcarboxyalky! Group having up to 6 carbon atoms means.

Preferred acyclic compounds of the formula XV are those in which R ₁ , R 2 and R 1 together have a total of 6 to 15 carbon atoms and R has the values given above as preferred for the cyclic sulfoxides and sulfones. Typical compounds of the formula XIV are listed in Table VI below.

Table VI

n-Hexyl-1 _r 2-diethylcyclohexylsulphone isopropyl-2,5-dimethylcyclohexylsulphone n-hexyl-1-isobutylcyclohexylsulphoxide p-menth-3-yl-n-butylsulphoxide
p-Menth-3-yl-ethylcarboxymethyl sulfoxide tert-butyl-S ^ S-trimethylcyclohexyl sulfone p-Menth-3-yl-carboxymethyl sulfoxide

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509833/0596

Methyl-2, e-dimethylcyclohexyl sulfone Methyl 2,6-dimethylcyclohexylsulfoxide-p-menth-3-yl-2-hydroxyethylsulfoxide n-Butyl-1- ± sopentyIcyclohexylsulfoxid n-Hexyl-2-n ~ butylcyclohexyl sulfoxide p-menth-3-yl-methyl sulfone Isopropyl-2-methylcyclohexyl sulfoxide Isopropy1-3-methylcyclohexyl sulfoxide Methyl 2,5-dimethylcyclohexyl sulfoxide Methyl-2, S-dimethylcyclohexyl sulfone n-Octyl-2-ynethylcyclohexyl sulfoxide n-butyl-1-isopentylcyclohexyl sulfone

Typical acyclic sulfones and sulfoxides of the formula XV are listed in Table VII.

Table VII

3-methylpent-3-yl-l-äthylbutylsulfoxid 2-methylnon-3-yl-n-propyl sulfoxide · S-methylhex-S-yl-n-octylsulfoxid 2, 6-dimethylhept-4-yl-2-hydroxyäthylsulfoxid 2.3 -Dimethylbut-4-yl-n-hexyl sulfoxide 3-ethylpent-3-yl-n-butyl sulfoxide

2-methylhept-3-yl-n-hexyl sulfoxide '

2, 6-dimethylhept-4-yl-sec-butylsulfoxide 2-methylbut-3-yl-sec-butyl sulfoxide 3,4,5-trimethylhex-4-yl-n-butylsulfoxide

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50983 3/05 96

2,3-Dimethylbut -2-yl-sec-butyl sulfoxide 2-Me thy lhept ~ 4-yl-n-butyl sulfoxide

2-methylhex-3-yl-n-butyl sulfoxide

4-n-propylhept-4-yl-n-propylsulfoxide 2,4-dimethylhept-4-yl ~ n ~ propylsulfoxide 2 , 5-dimethyloct-5-yl-n-propylsulfoxide 3-methylpent-3-yl-2'- ethoxycarbonylethyl sulfoxide 3-methylpent-3-yl-2'-hydroxyethyl sulfoxide hex-3-yl methyl sulfoxide

3-methylhept-5-yl-sec-butyl sulfoxide 3-methylhex-3-yl-isopentyl sulfoxide

3-methylhept-4-yl-n-butyl sulfone

3-ethylpent-3-yl-n-butyl sulfone

3-methylpent-3-yl-n-hexyl sulfone

2-methylhex-3-yl-n-butyl sulfone

2-methylnon-3-yl-propyl sulfone

Other suitable compounds of the formulas XIV and XV are described in German Offenlegungsschrift No. 2,334,985, the content of which is incorporated here will.

Phosphine oxides

The useful as Geschmacksmodifizierinittel phosphine oxides according to the invention are those of formula II, wherein it is required that at least one of the groups R, R _g and R ₆ a branch in einerOV-, _ß _ or ^ '- position with respect to having the phosphorus atom. For the avoidance of doubt, it should be noted that the concept of branching into the

- 41 509833/0596

This context is intended to include cyclic structures as well as branched-chain acyclic groups, ie this term applies to compounds in which either R ₅ and R _ß denotes a cycloalkyl group, the carbon atom of R ₅ or R, being in the ^ -position with respect to the phosphorus atom Is part of the ring and is therefore considered to be "branched". Preferably, R _4, R r and R, of such a nature that in each case 2 when taken together, have a total of at least 6 carbon atoms. Compounds of highest activity, which are particularly preferred according to the invention, are those in which R _{4 is} a straight-chain alkyl group with 4 to 8 carbon atoms, more specifically with 5 to 8 carbon atoms, R- is a branched-chain alkyl group with 3 to 5 carbon atoms and especially an isopropyl- , sec-butyl, isobutyl or isopentyl group and R _{6 is} an alkyl group, preferably a branched-chain alkyl group, with 3 to 6 carbon atoms, preferably 4 or 5 carbon atoms, or a cyclopentyl group, where R ₄ , R ₅ and R, a total of 12 have up to 18 carbon atoms.

The phosphine oxides used according to the invention can easily be prepared in a conventional manner. If two alkyl groups are the same, then _{dialkylphosphinyl chlorides, R 3} POCl, can be obtained by the action of thionyl chloride on tetraalkyldiphosphine disulfides or, preferably, by the action of chlorine on secondary phosphine oxides (made from Grignard reagents and diethyl phosphite).

- 42 -

509833/05 96

These dialkylphosphinyl chlorides react with Grignard reagents to form the desired tertiary phosphine oxides.

If all three alkyl groups of a tertiary phosphine oxide are different, then the following route is satisfactory. A Grignard reagent, RtIgX, is reacted with diethyl chlorophosphite to give ethyl alkyl phosphinite. This latter compound is reacted with a Grignard reagent, R ¹ MgX, to give the unsymmetrical secondary phosphine oxide, RR ¹ P (O) H. Tertiary phosphine oxides can be prepared from these secondary phosphine oxides as described above.

Representative phosphine oxides of the formula II, which according to the The present invention are listed in Table VIII. Other such connections can be found in DT-OS 23 45 156, to which reference is made here.

Table VIII

tert-butyl-n-hexyl-isopentylphosphine oxide, diisobutyl-n-hexylphosphine oxide
n-hexyl-cyclopentyl-isopropylphosphine oxide isobutyl-sec-butyl-n-heptylphosphine oxide sec-butylisopropyl-n-heptylphosphine oxide n-hexyldiisopentyl-phosphine oxide
n-butyl-n-heptyl-1-methylbutylphosphine oxide

- 43 -

5098 3 3/0596

250355g - 43t

n-pentyldicyclopentyl phosphine oxide

Diisobutyl-n-nonylphosphine oxide

p-menth-3-yl-di-n-propylphosphine oxide sec-butyl-isopropyl-n-octylphosphine oxide Diisobutyl-1-methyl-n-heptylphosphine oxide n-butyl-isopropyl-2-ethyl-n-hexylphosphine oxide. Di-n-butyl-cycloheptylphosphine oxide

Tri- (2-methylbutyl) phosphine oxide

Triisopentyl phosphine oxide

n-heptyl isopropyl isopentyl phosphine oxide

acyclic secondary and tertiary alcohols

When in formula I X is the group OH, a preferred group of taste modifiers is identified by acyclic secondary and tertiary alcohols of the general formula XVI represents:

c -oh

viorin R _{111 is} a hydrogen atom or a C, -C "-Alky! group and

and R _{113 are} each C ₂ -C ₅ -alkyl groups, i) when R _{111 is} a hydrogen atom, at least one of the groups R ₁₁₂ ^{and R} n3 is ^a branched-chain group, and

- 44 -

509833/0596

250355S - 44 -

ii) R ₁₁₁ / ^R ii2 ^{un <} ^ ^R 113 ^{together have} a total of 7 to 12 carbon atoms.

Secondary and tertiary alcohols of the formula XVI with physiological The refrigeration activity and usefulness for the invention as a taste modifier are also detailed described in DT-OS 23 16 999.

Preferred acyclic alcohols are secondary alcohols in which R ,,, is a hydrogen atom, R ,,, ^un ^ ^R n3 together have 7 to 9 carbon atoms and at least one of the groups R ,,, ^{un <} 3 R ₁₁ O has a branch in one ⁵ ^ - or ß-position with respect to the carbon atom _t to which the OH group is attached, as well as tertiary alcohols, where Ri _{11 is} a CjC ^ -alkyl group, R ₁₁₁ * ^R n2 ^unc ^ together have 9 to 12 carbon atoms and at least one of the groups R ₁₁ O ^and R _{113 has} a branch in a ™ or β position with respect to the carbon atom to which the OH group is bonded.

The acyclic alcohols of formula XVI can easily be according to conventional methods, such as by reduction of the correspond the ketones.

Typical alcohols of Formula XVI are listed in Table IX.

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509833/0596

Table IX

3-ethyl-4-methyl-3-hexanol 2-methyl-3-isopropyl-3-hexanol 4-isopropyl-4-heptanol 2,4-dimethyl-3-ethy1-3-pentanol 2-methyl-3-n- propyl-3-hexanol .2,4-dimethy1-4-heptanol 2,5-dimethy1-3-hexanol 3-ethyl ~ 4-methyl-3-hexanol 3,3,4,5-tetramethy1-4-heptanol 2, 2, 4-Trimethy1-4-heptanol, 2,6-dimethyl-4-heptanol 2-Methy1-4-heptanol, 2,4-dimethyl-3-hexanö3 2-methyl-3-isopropyl-3-pentanol 2, S-dimethyl -S-isopropyl-S-pentanol 2,4-dimethyl-3-ethyl-3-hexanol 2,5-dimethyl-3-isopropyl-3-hexanol 4-ethyl-2-methyl-4-octanol 2-methyl-1-4 -heptanol 2-heptanol Methy1-5-2,2,3-trimethyl-3-hexanol 3,4, 5-trimethyl-4-heptanol

Other acyclic alcohols which can be used according to the invention are listed in DT-OS 23 16 999, referred to here.

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509833/0596

cyclic alcohols

Another group of preferred compounds useful in accordance with the invention are cyclic alcohols generally Formula XVII:

wherein ρ is 0 or an integer from 1 to 5 and R and y are as defined above. The values for p, R and y should be such that the compound 10 to 14 is carbon contains atoms and that if ρ 1 and y 2 and one of the groups R is an isopropyl group in a 2-position in Ring with respect to the OH group and the other group R is a methyl group, the methyl group is in a 1, - 2-, 3-, 4- or 6-position in the ring with respect to the OH group. ·.

Cyclic alcohols of the general formula XVII with physiological Cooling activity and usefulness as a taste modifier according to the invention are in DT-OS 23 17 000, 22 03 947 and 24 58 562, referred to here. is taken.

Preferred cyclic alcohols are those with alkyl substituents in a 1- or 2-position in the ring and especially with

- 47 -

5 09833/0596

a secondary group such as an isopropyl or sec-butyl group. Preferably ρ has the value 1, 2 or 3.

Examples of suitable cyclic alcohols for use according to the invention are summarized in Table X.

Table X

2, S-diisopropylcyclohexanol
2-tert-butyl cyclohexanol
2-ethyl-1-ispropylcyclohexanol
1-isopentylcyclohexanol
1-sec-butyl-2-methylcyclohexanol
1-ethyl-2,6-dimethylcyclohexanol

l / S-Dimethyl-1-isopropylcyclohexanol- (3-methy! menthol) 1-ethyl-5-methyl-2-isopropyl-cyclohexanol (3-ethylmenthol} ln-propyl-2-methyl-cyclohexanol
1,2-diethy / cyclohexanol
1-methyl-2-isopropyl-cyclohexanol
1-n-butylcyclohexanol

2-n-propylcyclohexanol. "

2-isobutyl-5-methylcyclohexanol
in-propyl-S-methylcyclohexanol
l-isopropylcycloheptanol
2-ethylcyclooctanol
1-ethyl-3-methylcycloheptanol
1-methyl-2-isopropylcyclooctanol

2-sec-butylcyclopentanol -... · -...- ■

- 48 -

509833/0596 '■ ·

l-isopentylcycloheptanol

2-n-propylcycloheptanol

1,2-diethylcyclooctanol

2,6,6-TrimethyIcycloheptane ^

1,2,6,6-tetramethylcycloheptanol

l-iLthylcyclodecanol

2,4,4-trimethylcyclopentanol

l-sec-butyl-cycloheptanol

1- (2'-Jithylbuty 1) -cycloheptanol

2 ~ isopropylcyclooctanol

3,3,5,5-tetramethyl / cyclohexanol

Methylol compounds

Methylol compounds (instead also as substituted Methanols) with physiological cooling activity and usefulness as a taste modifier according to the Invention are described in DT-OS 22 03 947 and 24 39 770, the content of which is included here. You can easily be prepared for example by reducing the corresponding carboxylic acid or the corresponding ester.

Preferred methylol compounds for use in accordance with the invention have the formula XVIIT:

XVIII ^f

Λΐ6

- 49 -

5 09833/0596

wherein R ,,, a hydrogen atom or a C ₃ -Cg alkyl group,

R- and R ,, g taken separately are each C 1-6 alkyl groups or taken together an alkylene group, optionally contains a HydroxyIsubstituenten, mean and

R ,, ^, R-JiC and R-ijg together have a total of 6 to 14 carbon atoms own.

Preferred compounds of the formula XI for use according to the invention are those in which Rtj // ^R H5 ^{and <} ^ ^R 116 are each alkyl groups, especially those compounds in which at least one of these groups has a secondary or tertiary structure and those compounds in which R ,, . denotes an alkyl group and R ..- and R.,., are linked to one another to form an alkylene group.

Suitable methylol compounds for use in accordance with the invention are listed in Table XI below?

Table XI

p-menth-3-yl-methanol (3-hydroxymethyl-p-menthane) 2,4-dimethylpent-3-yl-methanol
3-ethyl-2-methylpent-3-yl-methanol
3-ethyl-2,4-dimethylpent-3-y! -Methanol (1-isopropylcyclohexyl) -methanol
(1-Isopropyl-2-methylcyclopentyl) methanol (2-hydroxy-p-menth-3-yl) methanol

- 5o -

509833/0596

- 5ο

(3-Hydroxy-p-menth-2-yl) -methanol (2-Hydroxymethy! Menthol) 2,4, e-Trimethylhept ^ -yl-niethanol

2-sec-Butyl-3-methylpent ~ 2-yl-methanol (1-sec-Butylcycloheptyl) methanol

(2, 2,6-trimethyl / cyclohexyl) methanol

n-Hep-t-3-yl-methanol

3,4,5-tri-methylhept-4-yl-methanol

(1-Isopropylcycloheptyl) methanol

(2,2,6-trimethylcyclohexyl) methanol

(1-n-Buty1-2,3-diethylcyclohexyl) methanol

substituted ureas

Within the formula III there are three types of compounds, namely the substituted ureas in which Y is R-gR-gNCO, substituted amides in which Y is R., CO, and substituted sulfonamides in which YR _{3 is} SO ₂ . Of these three types of compounds, particularly effective taste modifiers are substituted ureas of Formula XIXi

. 117

XDI

Ve

wherein ride taken separately a hydrogen atom, a ^c i ~ ^c ₆ "alkyl group or a C ^ cycloalkyl group -CG, R. g, taken separately, a C ₃ -C, alkyl group or C -C. -Alkylcycloalky! group, a Cycloalkyl group or cycloalkylalkyl group, where Ri.19 ^{on one at 0} ^ "or ß-carbon

- 51 509833/0596

O
Il \ c - ^Ρ Ί20 - IT

atom is branched with respect to the nitrogen atom, which is also in the case of cyclic groups it is assumed if the carbon atom is in ^ - or ß-position to the nitrogen atom of the ring is

R ,, - and ring taken together a branched-chain alkylene- a group with 3 to 7 carbon atoms and have a branch on the $ - or ß-carbon atom with respect to the nitrogen atom and the chain optionally an ether - (- 0-) oxygen atom to have,

R ,, _ and R _{118 have} a total of 5 carbon atoms, regardless of whether they are separate groups or a group taken together,

R ,, and R g] ₂ O 9 taken ^etrennt each hydrogen, C- |! _Fi -C ~ alkyl, C_-C _fi -AlkylcycloalkyIgruppen-cycloalkyl or -Cyclöalkylalky groups, C ₁ -C ₁ -hydroxyalkyl, C ₂ -C . -Carboxyalkyl groups or C ₃ -C _lo -alky! Carboxy a lkylgruppen mean or, taken together, a straight-chain or branched C ₃ -C. -Alkylene group which can optionally be substituted by oxygen or an oxygen-containing group and / or optionally can contain ether oxygen, and where R _ _{r R} , R and R ₁₂ Q together have a total of 6 to 15 carbon atoms.

Substituted ureas of the formula XIX with physiological Cooling activity and usefulness as a taste modifier

- 52 -; 509833/0596 -

according to the invention are also described in British patent application 16 803/74.

Typical substituted ureas of the formula XIX, which according to of the invention are listed in Table XII:

Table XII

N, N-di-sec-buty1-N'-ethylurea N-cyclohexyl-N-isopropyl-N, N'-dimethylurea N, N-diisobutyl-N ', N'-dimethylurea N ₁ N- (I, 5- Dimethylpentamethylene) -N'-ethylurea iithyl-N- (N ', N' -disec-butylaminocarbony 1) -glycinate N, N-pi-sec-butyl-N '- (2-hydroxyethyl) urea N, N-heptamethylene -N ¹ -isopropylurea N-sec-butyl-N- (cyclohexylmethyl) -N'-ethylurea N-cyclopentyl-N-sec-pentyl-N ¹ -n-propylurea

^{Amides of the formula XX R} 117 also lie within the formula III

^R 118 ^/
wherein R 1, -, and R _{110 are} as defined above and R, _O1

11 / llo. LZL

Hydrogen atom, a C ^ -Cg alkyl group or alkenyl group, a C ₃ -C cycloalkyl group, C _{-C hydroxyalkyl group, C 3} -C ^ carboxyalkyl group or C ₃ -C _lo -alkylcarboxyalkyl

'- 53 -

509833/0596

group, a phenyl radical or a C ^ -C.-alkyl-, -alkoxy-, OH-, COOH- or NO ₂ ~ substituents. Phenyl radical, where, when R _{12 is} I ^e ^ ^ne C _fi -alkyl group, has this primary structure.

The acyclic amides of Formula XX, which are used as flavor iodifiers are useful according to the invention differ from those of formula VII. While the amides of the formula VII amides are secondary and tertiary alkanoic acids having 7 to 20 carbon atoms, the amides are the Formula XX Amides of straight-chain alkanoic acids with up to 7 carbon atoms, amides of branched-chain alkanoic acids with up to 6 carbon atoms and amides of cycloalkanoic acids and substituted alkanoic acids, none of which falls under Formula VII. The amides of the formula XX can however, generally by the same methods as those of Formula VII. Amides of the formula XX with Cooling activity and usefulness as a taste modifier are disclosed in British Patent Application 16803/74 described.

Typical amides of the formula XX which are useful in accordance with the invention are listed in Table XIII.

Table XIII

N-sec-butyl-N-cycloheptylpropionamide N, N-di-sec ~ butyl-3-methylbut-2-enamide -

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509833/0596

N- (diisopropylmethyl) -2-methylpropionamide Ν, Κ-di-sec-butylacetamide N-cyclohexyl-N-isopropylbutanamide N- (2,4,4-trimethylpenfc-2-yl) pentanamide N-propionyl-2,6-dimethyl piperidine.

N-acetyl-4-methyl-7-isopropylhexahydroazepine N, N- (I ¹ , 5'-dimethylpentamethylane) -propionaraid n-isopropyl-Nn-pentylpropionamide N- (1 _r 1,3,3-tetramethylbutyl) -formamide N- (Diisopropylmethyl) -cyclopropanecarboxamide N-sec-Butyl-N-cyclopropylmethylpropionamide N, .N- ^ (1,5-dimethy lpentamethy len) -cyclobutanecarboxamide N-isopropyl-N-isobutyicyclopentanecarboxamide N / N-disec-butylboxylcyclohexanecarboxamide N / N-disec-butylboxylcyclohexane -N- (cycloheptylmethyl) -propionamide N-tert-octylcyclohexanecarboxamide N-isobutyl-N- (1,2-dimethylpropyl) -p-nitrobenzamide Ν, Ν-diisopropylbenzamide Ν, Κ-di-sec-butyl-p-methoxybenzamide

Sulfonamides

Sulfonamides of the formula also lie within the formula III XXI

wherein R ,, _ and R ,, _{o are} as defined above and R _{100 is} a

4.1 / XXO X.ZZ

C, -C -alkyl group or a C.-Cg -cycloalkyl group,

- 55 509833 / 059S

where, when R. _{22 is} a C1- or C6-alkyl group, has this primary structure.

The sulfonamides of Formula XXI are different from those of the formula XII in the same way as the amides of the formula XX differ from the amides of formula VII. In other words, the sulfonamides of the formula XIII are derivatives secondary and tertiary alkanesulfonic acids with 6 to 19 Carbon atoms, while those of formula XXI are derivatives primary alkanesulfonic acids and branched-chain sulfonic acids with up to 5 carbon atoms and also of cycloalkyl sulfonic acids are »The sulfonamides of the formula XXI can easily be obtained from the corresponding acid chlorides and suitable Acids are produced.

Sulfonamides of Formula XXI with cooling activity and utility as taste modifiers according to the invention described in British Patent Application No. 16 803/74.

Typical sulfonamides of the formula XXI are listed in Table XIV:

Table XIV

N, N-di ~ sec-butyl methane sulfonamide
N, N-diisopropylethanesulfonamide

N, N- (1,5-dimethylpentanemethylene) ethanesulfonamide N-Isopropyl-N-cyelohexylethanesulfonamide

■ - 56 -

509833/0596 ■

N- (1,1,3-trimethylbutyl) ethanesulfonamide
N-isopropyl-N-isobutyl-n-propanesulfonamide

p-menthediol

If in the formula I x _{denotes OH or CH 2} OH, then R ₂ and R-, taken together, denote an alkylene group which bears an OH substituent. Where this is the case, a preferred group of taste modifiers according to the invention is represented by p-menthandiols of the general formula XXII:

XXII

where X is OH and where two OH substituents are bonded to different carbon atoms and at least one is in the 2 or 3 position.

p-Menthandiols of the formula XXII with physiological cooling activity are also described in DT-OS 22 03 273, on their Content is referred to here.

Typical p-menthandiols used according to the invention as taste modifiers are the following:

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5 0 9833/0596

2,3-p-menthane diol
2,6-p-menthane diol
2,5-p-menthane diol
3,5-p-menthane diol
3,9-p-menthane diol

acyclic carboxylic acids, their salts and esters

A final group of compounds with taste-modifying activity is represented by the formula XXIII:

XXIII R ₂ - C * - - COOS

ι ·

^IS 7

• j ί

wherein R is a hydrogen atom or a C -C -Alky! group, preferably a hydrogen or a C - * - C ^ -Alky! group, means,

R ₂ and R- each _{denote C, -C g} -alky! Groups, preferably C - C alkyl groups,

R ₁ , R ₂ and R ₃ together have a total of 6 to 18 carbon atoms and

R _{7 is} as defined above, both in terms of its broad and preferred meaning.

- 58 509833/0596

Preferred acyclic acids are those in which at least one of the groups R, / 1 * 2 and R_ is a branched-chain alkyl group is, preferably one with a branch in an OC or ß-position with respect to that marked with (*) Carbon atom.

Typical acids and esters according to Formula XXIII are listed in Table XV. They can be prepared by readily available methods, such as by .CO, introduction into the corresponding Grignard reagent.

Table XV

2-hydroxypropyl-3-methyl-2-isopropylpentanoate, 2'-hydroxyethy1-2,2-diethylbutanoate, 2-ethyl-3-methylpentanoic acid
2'-hydroxyethyl-2-isopropyl-3-methylbutanoate, 2'-hydroxyethyl-2-ethyl-2-isopropyl-1-3-methylbutanoate, 2-ethyl-2-methylbutanoic acid

3-methyl-2-isopropylpentanoic acid

1-ethyl-2-isopropylbutanoic acid

2-sec-butyl-2,3-dimethylpentanoic acid

3-methyl-2-isopropylbutanoic acid

2-sec-butyl-3-methylpentanoic acid

2-isobutyl-4-methylpentanoic acid

The use of the compounds according to the invention as Taste modifier is exemplified by the following

- 59 -

509833/0596

explained. The examples reproduce the results recorded by test groups with regard to the taste / with a control substance being tasted as a comparison sample in each test and a substance corresponding to the control sample , but with a content of a taste modifier according to the invention in the specified concentration. Aqueous solutions of the taste modifiers at the concentrations used in these examples were tasteless.

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509833/0596

Example T

1 ppm of N- (p-methoxyphenyl) -p-menthan-3-carboxamide was added to separate samples of an infusion of ground coffee (Sample A) and N- (1,1-dimethyl-2-hydroxyethyl) -p-menthane-3-carboxamide (Sample B) given.

Both samples were seasoned with a control sample compared. The taste results were as follows:

Sample A

less burnt less bitter more blended

Sample B

less bitter seniger strongly burnt less sour less drying

Example 2

1 ppm N- (p-methoxyphenyl) -p-menthane-3-carboxamide became added to an infusion of powder coffee and compared in terms of taste with a control infusion. The test sample possessed increased blending properties, an increased coffee taste and reduced bitter taste.

Example 3 ■ "

N- (1 ', 1' -Dimethyl-2 '-hydroxyethyl) -p-menthan-3-carboxamide added to milk at room temperature in an amount of 4 ppm. Compared to a control sample, the treated sample gave in the taste test decreased waxiness and decreased Sour taste, increased taste and increased creaminess.

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Example 4

N- (p-methoxyphenyl) -p-menthane-3-carboxamide (1ppm) became added to an infusion of powdered tea with sugar and lemon and compared with a control infusion. The treated sample possessed a sweeter taste, better blending properties and a sharper lemon taste.

Example 5 · ■ - ".-

2-Hydroxyethyl-p-menthane-3-carboxylate became a commercially available one Chewing gum added at 16 ppm. Compared with a control sample, the treated sample had a sweeter taste and stronger peppermint flavor. Similar results obtained with the same amount of N- (1 ', 1'-dimethyl-2 · - hydroxyäthy1) -p-menthancarboxamide.

Example 6

4 ppm N- (1 ', 1'-dimethyl-2'-hydroxyethyl) -p-menthane-3-carboxaraid were added to a commercial chocolate milk pudding. Compared to a control sample, the treated sample had a significantly stronger chocolate taste and sweeter Taste together with reduced sour taste and bitter taste and a less strong milk caseinate flavor.

Example 7

Powdered drinking chocolate was made using low-fat cocoa and low-fat dry milk. A mixture of N- (1 ' , 1'-dimethyl-2 · -hydroxyethyl) -p-menthan-3-carboxamide and

5 09833/0596

2-Hydroxyethyl-p-menthane-3-carboxylate was added. The dry powder was mixed with water to make a chocolate drink containing 3 ppm of the former compound and 1 ppm of the latter compound. Compared to a Control sample, the test sample had increased resinous chocolate property with less perception of dry particulate matter and less chalky dry feeling in the mouth.

Example 8

4 ppm of 2-hydroxyethyl-p-menthane-3-carboxylate were coated with chocolate added with low quality chocolate liquid. The resulting sample showed increased resinous chocolate property / a creamy feel in the mouth and an overall taste comparable to that of higher quality Chocolate liquid.

Example 9

3 ppm N- (1 ', 1'-dimethyl-2'-hydroxyethyl) -p-menthane-S-carbpxamide and 1 ppm of 2-hydroxyethyl-p-menthane-3-carboxylate were added to a commercially packaged vanilla pudding. In comparison with a control sample was the treated one. Pudding fuller and better cut, sweeter, more like egg cream and less starchy.

Example 10

An aqueous white flavor medium that shares all four basic flavors contained, namely sweet, sour, bitter and salty, was prepared as follows:

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Sodium chloride 0.92 8 g

Cane sugar 6,800 g

Citric acid (anhydrous) 0.252 g

Caffeine (anhydrous) 0.112 g

Water to 1000 ml

T ppm of various compounds became samples of this flavor medium added and the taste change was made compared to a control sample. The following changes in taste were noted:

Connection change of taste

p-menthane-3-carboxylic acid: sweet, delayed sour taste -

N-ethyl-p-menthanS-carboxamide sweeter

2-hydroxyethyl-p-menthane-3-carb- sweeter, less acidic oxylate

N- (p-menth-3-oyl) -glycine ethy ester sweeter, bitter

N- (1 ', 1 ^f -dimethyl-2'-hydroxyl saltier and pungent ethyl) -p-menthane-3-carboxamide

N-tert-butyl-p-menthane-3-carb- salty and bitter oxamide. ■

N- (p-Menth-3-oyD-glycine-n- more acidic and bitter propyl ester.

sweet, sour aftertaste butanamide

N-ethyl-2,3-dimethyl-2-isopropyl-- acidic aftertaste and butanamide tannic feeling in the mouth

N-ethyl-i-isopropylcyclohexane acidic and salty carboxamide

N-isopropyl-p ~ menthan-3-carb taste suppression and oxamid late onset of Ge

taste

N- (p-Menth-3-oyl) -morpholine sweeter

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N- (p-menthane-3-sulfonyl) morpholine

N-A thy 1-p-menethan-3-carboxaitiide (dl-axial)

5-isopropyl-2 dimethylcyclohexylsulfon,

n-hexylcyclopentylisopropylphosphine oxide

Isobutyl-sec-butyl-n-heptylphosphine oxide

N, N, 2-triethyl-3-methylpentanamide

N- (1 ', 1'-dimethyl-2-hydroxyethyl) -1,2-diethylcyclohexanecarboxamide

sec-butylisopropyl-n-heptylphosphine oxide

N, N-diethyl-3-methylpent-3-ylsulfinamide

N- (4-Hydroxy-3-methoxyphenyl) -p-menthane-3-carboxamide

N- (2'-acetoxy-1 ', 1'-dimethy1-ethyl) -p-menthane-3-carboxaniid

N, N-diethy1-p-menthane-3-carboxamide

N-Cyclohexy1-p-menthane-3-carboxamide more blended, stronger flavor, yeast-like taste

salty and bitter

cutie pie

bitter and fruity

sweet aftertaste

more oily or buttery
taste

metallic taste

delayed fruit taste fruity taste

delayed bitter taste sour aftertaste

less sour, peppery sour, salty

N-n-decyl-p-yn.enthan-3-carb-ox, amide

N / 1 -diisopropyl-2-methylcyclopentahcarboxamide

N- (1-ethyl-2-methylcycloheptanecarbonyl) glycine ethyl ester

N- (tert-butyl) -2-isopropylcycloheptane carboxamide

Triisopentylphosphine oxide sweeter, salty, sour
After your taste

acidic

salty, tannic feel in the mouth

sour, sour aftertaste

sweeter (syrupy), tannic feel in the mouth

509833/0596

Isobutyl-n-heptylcyclopentylphosphine oxide

Isobutyl sec-butyl-n-pentylphosphine oxide

n-heptylcyclopentylisopropyl * - phosphine oxide

N- (3,4-Dimethoxyphenyl) -p-menthane-3-carboxamide

N- (3,4-Dimethylphenyl) -p-menthane-3-carboxamide

N- (4-methylphenyl) -p-menthan-3-carboxamide

N- (3-Hydroxy-4-methylphenyl) -p-menthane-3-carboxamide

N- (p-menthane-3-carbonyl) -glutamic acid diethyl ester

2- (2'-Hydroxyethoxy) ethyl pmenthan-3-carboxylate

S-hydroxypropyl-p-menthane-S-carboxylate

p-menth-3-yl-di-n-propylphosphine oxide

Diisobutyl-n-nonylphosphine oxide delayed sour taste sour, salty

sweeter, tannic feel in the mouth

sweeter (syrupy)

sweeter, sour, salty, salt sensation in the mouth

acidic, astringent acidic (spicy)

bitter

sweeter, bitter

salty, astringent bitter

salty, salt water-like Sensation in the mouth

Diisobutyl-n-heptylphosphine oxide bitter, astringent

Example 11

An infusion of instant coffee was made using a commercially available Variety of instant coffee made. Separate portions of the infusion were sweetened with saccharin, and into one The sweetened portion was 1 ppm of N- (1 ', 1'-dimethyl-2'-hydroxyethyI) -p-menthan-3-carboxamide added. When tasted, this latter portion tasted pleasantly sweet and without a bitter aftertaste. The control sample had the bitter aftertaste,

50983 3/0596

which is commonly associated with saccharin when called artificial sweetener is used.

Example 12

An aqueous cane sugar solution was used as the standard sweetening solution manufactured. To separate samples of this solution, increasing amounts of various compounds were added, and the smallest Amount of connection that was required to make a noticeable It has been found to increase the sweet taste. The results were as follows:

link

tert-Buty1-n-hexylisopentylphosphine oxide Diisobutyl-n-hexylphosphine oxide isopropyl-n-hexylcyclopentylphosphine oxide —Sec-buty1-n-hexylphosphine oxide

Amount , µg / ml 1 1 8 0.5

Example 13

An O _r Oi m aqueous cane sugar solution was prepared and seasoned to taste, and it was found that at this concentration the sweet taste was imperceptible. Addition of the following compounds in the specified amounts to separate samples of the cane sugar solution resulted in solutions with a clearly perceptible sweet taste:

Compound amount ^ ug / ml

2 ^I -hydroxyethyl 2-isopropyl-3-methylbutanoate 2

2 ^f -hydroxyethyl-2-ethyl-2-isopropyl-3-methylbutanoate 3

2-ethyl-2-methylbutanoic acid 5

50 9 833/0596

Aqueous solutions of the three compounds in the specified concentrations had no taste

Example 14

The taste-modifying effect of a number of compounds was determined by comparing the taste of a so-called white taste _{medium r} i.e. a medium with a content of substances with all four basic flavors, namely, sweet, sour, bitter and salty, with the same medium, but with the content of Compound found at a concentration of 1 ppm.

The white flavor medium had the following composition

Sodium chloride 0.928 g

Cane sugar 6,800 g

Citric acid (anhydrous) 0.252 g,

Caffeine (anhydrous) 0.112 g

Water to 1000 ml

The modified taste due to the following compounds was determined with the control sample by taste panelists determined as follows:

Investigated compound effect

2-Methyl-3-isopropyl-3-hexanol is more sweeter and salty

taste

2,4-Dimethyl-3-ethyl ~ 3-hexanol, stronger sweet taste

2,5-Dimethyl-3-isopropyl-3-hexanol is more bitter and salty taste

2-Methyl-3-isopropyl-3-decanol has a stronger sour taste 3-ethylmenthol syrupy aftertaste

50983 3/059 6

Example 15

A test similar to that described in Example 14 was made carried out, but with the exception that a basic taste

_3

medium with a content of 1.5x10 m citric acid and 2 × 10 m saccharin (sodium salt) in aqueous solution was used instead of the white flavor medium of Example 14, and the following compounds were tested at a concentration of 1 ppm with the following results:

effect

stronger sour taste

slight increase in sour taste

Compound used 1-see-butylcycloheptanol 1-iso-propylcycloheptanol

Example 16

A solution of 0.01 M cane sugar was used in terms of taste with solutions of 0.01 m cane sugar, each of which also contains one of the compounds mentioned below in a concentration of 1 ppm. The solutions containing the compounds had the following modified taste:

Connection used

1- (2-ethylbutyl) cycloheptanol 4-ethyl-2-methyl-4-octanol 2-methyl-3-isopropyl-3-decanol, 6-ethyl-3-decanol

1-n-butyl-2,3-dimethylcyclohexy / methanol

509833/0596

effect

Improvement of the sweet taste

slight improvement in the sweet taste

slight improvement in the sweet taste

slight improvement in the sweet taste

slight improvement in the sweet taste

2,2, e-Trimethylcyclohexylmethanol slight improvement of the

sweet. Taste

2-sec-butylcyclopentanol slight improvement in the

sweet taste

p-Menthyl-3-methanol slight improvement of the

sweet taste and slightly syrupy aftertaste

Example 17

The effect of the following compounds at a concentration of 1 ppm on the taste of a solution containing 2 × 10 m saccharin was determined by comparing a solution containing the compound with a control saccharin solution. The results were the following:

Investigated compound effect

1-methyl-2-isopropylcyclooctanol Reduction of the bitter

tasty, metallic aftertaste

2,2,6-Trimethylcyclohexylmethanol slight improvement of the

sweet taste

2,2-diethyl-3-methylbutanol slight improvement of the

sweet taste

In addition, the compound had 2-isopropylcyclooctanol in one Concentration of 1 ppm has very little improving effect

—5 to the sweet taste of a 4 χ 10 M saccharin solution, if the test was carried out in the same way. .

Example 18

i-Isopropyl-2-methylcyclophenylitiethanol was used in one concentration of 0.5 ppm incorporated into a sample of carbonated ginger beer (ginger ale). In comparison with an untreated one Sample of the drink showed that the

509833/0596

Sample containing taste modifiers has a sharper dry one Had an aftertaste.

2,5-diisopropylcyclohexanol gave a similar drink a more blended taste with a sharper ginger aftertaste when added at a concentration of 0.3 ppm became.

Example 19

0.5 ppm of the compounds mentioned below were separated Samples of a commercial carbonated cola drink added, and the taste of the treated samples was compared with that of the untreated beverage. The results were as follows:

Compound used 2-methyl-1-4-heptanol 2,4-dimethyl-4-heptanol 1-isopropylcycloheptanol

effect

Cola taste sharper, more blended

slight increase in the sweet taste, sharper

Citrus taste sharper, suppression of the aftertaste of the untreated drink, stronger sweeter
aftertaste

Example 20

A coated chocolate was made from a series of samples, each of which contained one of the compounds listed below in the specified concentration. The taste Each sample treated in this way was compared with that of a control sample, the following results being obtained:

509833/0596

Connection used

3,3, 5,5-tetramethylcyclohexanol

1-isopropyl-2-methylcyclopenty / methanol

2,6-dimethyl-4-heptanol

2-tert-butyl cyclohexanol

Example 21

Concentration (ppm)

0.5

0.5

0.5

0.25

effect

Enhanced chokqlade and creamy taste, diminished Fat taste and reduced fat texture

slightly improved, fuller chocolate taste

slightly improved chocolate taste

slightly softer, improved chocolate taste

1-Isopropylcyclohexylmethanol was used in a concentration of 0.3 ppm added to a commercial lemon-lime liqueur. The taste of the liquor thus treated was softer with stronger Lime flavor and stronger citrus aftertaste in comparison with an untreated liqueur.

Example 22

2,4,4-Trimethylcyclopentanol became a milk sample in a Concentration of 0.2 ppm added. The milk so treated. . had a stronger creamy aftertaste compared to an untreated control sample.

Example 23

In a test of the taste-modifying effects of a series of compounds in commercially available dietary milk chocolate were samples of the chocolate by incorporating one at a time of the following compounds in a concentration of

509833/0596

0.5 ppm treated. A taste comparison of the treated Chocolate with untreated samples gave the following results:

Compound used 2-ethylcyclooctanol

2, -2,4-trimethyl-4-heptanol, 2,4,4-trimethylcyclopentanol

effect

stronger chocolate taste, less milk oversaturation

increased chocolate taste, softer, less oversaturated texture

faster onset of chocolate taste, diminished creamy aftertaste

In a similar test, but with a standard full chocolate gave 1-ethyl-S-methylcycloheptanol in one concentration of 0.5 ppm a chocolate with an improved, less tart, more rounded, bitter, resinous chocolate aftertaste, and 3-hydroxy-p-menth-2-yl-methanol at a concentration of 0.5 ppm gave a chocolate with softer, less bitter chocolate taste and a less bitter aftertaste.

Example 24

An infusion of powdered tea with sugar and lime was prepared in the form of several samples, and for each of these samples were added one of the compounds mentioned below was added in a concentration of 0.1 ppm. Comparison of the taste of the treated Drinks and from untreated control samples produced the following results:

509833/0596

Compound 6-ethyl-3-decanol used

i-sec-butylcycloheptanol

2-isopropylcyclooctanol

Example 25

effect

stronger sweet syrupy taste, earlier onset of sour taste, less bitter aftertaste

earlier onset of taste, slight increase the tannin taste, less bitter metal-like macho taste

less sour taste, less bitter metal-like aftertaste

Infusions of commercially available powder coffee were made, and each sample contained 0.1 ppm of one of the following compounds: 2-sec-butyl-2,3-dimethyl-1-pentanol and 2,2,6-trimethylcyclohexylmethanol. In comparison with a control infusion, each of the infusions containing one of the compounds gave a faster one Onset, increased flavor note and flavor duration of the coffee taste, while the taste and the aftertaste were less bitter.

Example 26

2-Ethyl-i-isopropylcyclohexanol was used in a concentration of 0.2 ppm to a commercially available powdered drinking chocolate added that had been put on in hot milk. In comparison with the drink similarly prepared but without the additive according to the invention possessed the treated drink a sweeter, creamier and softer chocolate taste.

If 1-isopropylcycloheptylmethanol tested in the same way was, its effect on the drink was in a concentration

509833/0596

tion of 0/1 ppm such that you get a creamier taste got with earlier onset.

Example 27

A commercial chocolate and malt drink was made according to dressed in hot milk according to the manufacturer's instructions. 0.4 ppm Each of the compounds listed below were added to samples of this beverage, and a taste comparison with untreated control samples gave the following results:

Connection used

1,2,6,6-tetramethylcycloheptanol

2,4-Dimethylpent-3-yl-methanol Example 28

■ Effect

sweeter, slight diminution of the chocolate and malt taste

sweeter, increase in the malt taste, softer chocolate taste

The following compounds were made in the indicated medium and tested in the specified amount. The flavor modification is given in the fourth column.

link

Test medium

N-sec-butyl-N-grated carcycloheptyl potatoes propionamide

N, N-di-secbutyl-3-methyl-but-2-enamide

Salad cream

Amount of compound added (ppm)

Chocolate dessert

effect

a little creamier

slightly sharper taste

stronger chocolate taste

509833/0596

~ 75 -

N- (diisopropylmethyl) -2-methylpropionaramide

Vanilla pudding 0/1

Chef's chocolate

N, N-Di-sec-bu-lemon jelly tylpropionamide

N- (2,4,4-trimethylpene t ~ 2 ~
yl) propionamide

2 χ 1O " ⁵ m saccharin

Ν, Ν-Di-sec-bu- 2 χ 1θ " ⁵ m tylacetamide saccharin

N-Cyclohexyl-Linome-Powder-N-isopropylbutee
tanamide

N- (2,4,4-trimethylpent-2-yl) pentanamide

Kochs choko1ade

N-propionyl-2,6-dimethylpiperidine

N- (2,2-dimethylpropio-
ny1) -2 f 6-dimethylpiperidine

Bottled beer

0.01 m cane sugar

Strawberry jelly

N-acetyl-4-me- vanilla pudding thyl-7-isopro-

pylhexahydro-

azepin

N, N-Di-sec-bu-grated Kartylmethansu1-potatoes
fonamid

N-Cyclohexyl-Schokoladenge-N-isopropyltränk
N ¹ , N'-dimethy lh ar η s tof f

slightly stronger vanilla flavor

stronger bitter aftertaste

sharper lemon flavor

sweet, improved aftertaste

something sweeter

sharper citrus taste

prolonged aftertaste

stronger bitter aftertaste

something sweeter

slightly stronger taste

sweeter, especially in the aftertaste

better aftertaste

slightly sweeter and stronger chocolate taste

509833/0 5 96

N / N-Diisobu- 0.01 m pipe- 1.0 a bit sweeter

tyl-N ¹ , N'-di- sugar

methyl urine

N-Ethyl-N ¹ - Vanilla dessert 0.1 slightly sweeter (2,3-dimethyl aftertaste

proyp) urea

example

The following compounds were added to the specified media, and the taste was compared to a control sample,

N- (2,3-Dimethyl-2-isopropylbutanoyl) -glycine ethy ester 0.5 ppm in limonepowder drink resulted in a somewhat sweeter and astringent character.

N-ethyl-3,3-dimethyl-2-isopropylbutanamide

0.2 ppm in powdered orange drink gave a more natural orange taste,

N-pentyl-3-methyl-2-isopropylbutanamide

0.5 ppm in lime powder tea resulted in a better overall taste with increased tea flavor and more natural lime character,

3-Hydroxypropy1-3-methy1-2-isopropylpentanoate 0.3 ppm in a commercial oxtail soup increased the taste of meat and herbs and decreased the taste of salt and vegetables.

2-hydroxyethyl-2,2-diethylbutanoate 0.2 ppm in beer gave a prolonged bitter aftertaste with very little effect on the main taste.

509833/0596

2-Ethy1-3-methylpentanoic acid

0/5 ppm in Limonepulvert.ee decreased the lemon taste and enhanced the sweet taste.

N-sec-butyl-N-isobutyl-N'-isopropy! Urea 0/4 ppm in lime drink slightly increased the sour taste and overall the lime taste.

N- (2/4-dimethyl ~ 2-isopropylenetanoyl) pyrrolidine

0/4 ppm in orange drink gave a stronger taste and sweetness stronger orange flavor.

N-isobutyl-N- (2-ethyl-n-propyl) -N'-cycloprppy / urea 0.2 ppm in powdered lime tea gave a stronger tannic taste.

Example 30

1. 0/1 ppm N- (p-methoxyphenyl) -p-menthane-3-carboxamide +

0/5 ppm 2-hydroxyethyl-p-menthane-3-carboxylate in orange juice gave an improved orange taste.

2. 0/5 ppm N / 2/3-trimethyl-2-isopropylbutanamide +

0.5 ppm 2-hydroxyethyl-p-menthane-3-carboxylate in orange juice gave an improved taste and enhanced sweet aftertaste.

3.5 µg N / 2,3-trimethyl-2-isopropylbutanamide in a cigarette gave a stronger tobacco taste.

4.5 µg of N-tert-butyl-p-menthane-3-carboxamide in a cigarette gave a milder, less pungent taste.

5.5 / ug N, 2 _/ 3-trimethyl-2-isopropylbutanamide in 1 g of pipe tobacco gave a milder taste,

509833/0596

6. 5 µg of 2-hydroxyethyl-p-menthane - 3'-carboxylate in 1 g of pipe tobacco gave a more fragrant smoke, and the taste was less pungent,

7. 2 µg di-sec-butyl-n-heptylphosphine oxide in a cigarette gave a slightly milder, better taste.

8. Yielded 2 / ug of 1 ^ isopropylcycloheptanol in a cigarette a slightly stronger taste.

9.2, Ν-di-sec-butylacetamide in 1 g of pipe tobacco yielded a fuller and softer taste.

10.5 g of Ν, Ν-di-sec-butylacetamide in 1 g of pipe tobacco resulted a stronger taste.

11. 5 µg of 2,4-dimethyl-3-ethylhexan-3-ol in 1 g of pipe tobacco a milder and better taste.

You can also use similar taste-modifying effects get all the other compounds described above that are capable of the cold receptors of the human nervous system To stimulate the body.

509833/0596

Claims (25)

Claims 1. Method of modifying the taste to have taste Ingestible substances or preparations including tobacco, characterized in that one is in the substance or the preparation a compound other than menthol that stimulates the cold receptors of the body's nervous system, in abundance below the threshold of practical physiological cooling activity. 2. The method according to claim 1, characterized in that one at least one compound of the general formula fi IU-C-X - ^R 3 used, wherein R is a hydrogen atom or a C ^ -C ^ -alkyl group, R ₂ and R _{3 taken} separately each denote alkyl groups or cycloalkyl groups with up to 6 carbon atoms or R2 and R-> taken together are a straight-chain or branched-chain C ₄ -C. ., - denote an alkylene group, where, when R- is a hydrogen atom, the alkylene group is branched on a carbon atom in β- or γ-position with respect to the group X, R ₁ / R ₂ ^and <3 Ro together a total of 6 to 18 carbon atoms and X is the group COOR ₇ , CONRgR ₉ , SO _x NRgRn or SO L _n , where R _{7 is} a hydrogen atom, an alkali or alkaline earth metal, an ammonium, alkyl or hydroxyalkyl-substituted ammonium group or 'a hydroxylalkyl, hydro- 509833/0596 xyalkoxyalkyl-, carboxyalkyl or Alkylcarboxyalkylgruppe having up to 12 carbon atoms, R "and R _g -genommen separately are each hydrogen or alky! groups, with up mean hydroxyalkyl groups, carboxyalkyl groups or Alkylcarboxyalkylgruppen to 12 carbon atoms, wherein when Rg is a hydrogen atom, R _{q can} also be a cycloalkyl group with up to 8 carbon atoms, such as an unsubstituted or hydroxyl group. C ₁ -C alkyl or. C -, -C. -Alkyloxy substituted phenyl group or benzyl group, R "and Rg taken together represent an alkylene group with up to 12 carbon atoms, where the carbon atom chain can optionally also be interrupted by oxygen atoms or the group -NH-, R ^ ₀ a Denotes alkyl, hydroxyalkyl, carboxyalkyl or alkylcarboxyalkyl group with up to 12 carbon atoms and χ is 1 or 2. 3. The method according to claim I _1, characterized in that at least one compound of the general formula ^R 3 used, wherein R _{1 is} a hydrogen atom or a Cj-Cg-alkyl group, R ₂ and R _{3 taken} separately each denote alkyl groups or cycloalkyl groups with up to 7 carbon atoms or R ₂ and Rg taken together straight-chain or branched-chain C ₄ -C ₁₁ alkylene groups mean, which may contain a hydroxyl substituent, where 509833/0596 a) if R. is a hydrogen atom, the alkylene chain on one Carbon atom in a ß- or ^ position with respect to "the Group X is branched and b) when R is a hydrogen atom and X is a hydroxyl group, the cyclic group of the formula ^R 2 ~ ^ ~ ^R 3 is not a p-menth-3-y! group, X is OH or CH ₂ OH and R ₁ , R ₃ and R ₃ together comprise a total of 6 to 18 carbon atoms. 4. The method according to claim 1, characterized in that at least a compound of the general formula Rr - P = 0 used, wherein R. is a C ₃ -C ₂₀ -alkyl group, R ^ is a CU-Cg-alkyl or cycloalkyl group, Rg is a C ^ -Cg -alkyl group or Co-Cß-cycloalkyl group or -alkylcycloalkyl group, where at least one of the groups R, Rj. and Rg on the carbon atom is branched in a ά- , ß- or Γ-position with respect to the phosphorus atom, and R-, R- and R- together have a total of 10 to 24 carbon atoms. 5. The method according to claim 1, characterized in that at least a compound of the general formula. ^R 12 used, wherein R _{11 taken} separately is a hydrogen atom,
a Cj-Cg-alkyl group or a Cj-Cg-cycloalkyl group means 509833/0 596 tet, R _{12 taken} separately denotes a C ₃ ^ -C _{1 Q} -alkyl group or C ₃ -C ₁₀ -alkylcycloalkyl group, -cycloalkyl group or -cycloalkylalkyl group, where R _ is branched on a ^ - or ß-carbon atom with respect to the nitrogen atom and these The requirement is also met in the case of cyclic groups if the carbon atom in the d- or ß-position to the nitrogen atom is part of the ring, R ₁₁ and R ^ p taken together mean a branched-chain alkylene group with 3 to 7 carbon atoms, the alkylene group on the d - Or ß-carbon atom branched with respect to the nitrogen atom and the chain optionally contains an ether oxygen atom (-0--), R ₁₁ and R _12, regardless of whether they represent separate groups or are taken together, have a total of at least 5 carbon atoms and YR ₁₃ CO -, R ₁₄ SO ₂ - or R *, -R ₁ , NOC- is where R _{13 is} a hydrogen atom, a Cj-Cg-alkyl group or -alkenyl group, a C ₃ -Cg -cycloalkyl group, a C ^ C ^ - Hydroxyalky L group, a C ₂ -C ₁ Q-carboxyalkyl group, a C ₃ -C ₁₀ -alkylcarboxyalkyl group, the phenyl radical or a phenyl radical containing Cj-C.-alkyl or alkoxy, OH, COOH or N0 ₂ substituents , where, when R ₁ - is a C ^ -alkyl group, this primary structure is, R 4 is a Ci-Cg-alkyl group or C ₃ -C, -cycloalkyl group, where, when R _{14 is} a C ₅ - or Cg-alkyl group means that this primary structure is R ₁₅ and R _{16 taken} separately hydrogen atoms, Cj-Cg-alkyl groups, C ₃ -Cg -alkylcycloalkyl groups, - ^ cycloalkyl groups or cycloalkylalkyl groups, Cj-CiQ-hydroxyalkyl groups, C ₂ -C. _Q denotes carboxyalkyl groups or C ₃ -C ₁ -alkylcarboxyalkyl groups or, taken together, denotes a straight-chain or branched-chain C ₃ -C ₁₀ -alkylene group 50983370596 mean which can optionally be substituted by oxygen or an oxygen-containing group or can contain an ether oxygen atom, and R ₁₁ / R ₁₉ and Y have a total of 7 to 16 carbon atoms. 6. The method according to claim 1, characterized in that at least ¹ compound of the general formula is used used, where η is O or an integer from 1 to 6, R is a C .. -C alkyl group, y is an integer from T to 4, where at least one group R is in a 1-, 2- or 3-position of the ring, R _{28 taken} separately denotes a hydrogen atom or an alkyl or hydroxyalkyl group with up to 12 carbon atoms, R "taken separately denotes a hydrogen atom, an alkyl, hydroxyalkyl, carboxyalkyl or alkylcarboxyalkyl group with up to Means 12 carbon atoms, where, when R ₂ g is a hydrogen atom, R _2g also contains a cycloalkyl group with up to 8 carbon atoms, a phenyl radical, a benzyl radical or hydroxy, C ₁ -C alkyl or -C ₁ -C ₄ alkoxy substituents can mean phenyl or benzyl radical having at most 12 carbon atoms, and R _"R and R" taken together form a Älkylengruppe g up means 12 carbon atoms, optionally DIE also an oxygen heteroatom may contain. 7. The method according to claim 1, characterized in that at least a compound of the general formula 509833/0596 - where R "o and R _{oq are} as defined in claim 6. 8. The method according to claim 1, characterized in that at least a compound of the general formula • ^R 23
^l 24 used, in which m is 2 or 3, at least one of the groups R 2 and R_. a C ₁ -C _g -alkyl group and the other is a hydrogen atom or a Cj-C ^ -alkyl group and R " _a and R are as defined in claim 6. 9. The method according to claim 1, characterized in that at least a compound of the general formula ?1 R ₂ -C-CONR ₂₈ R ₂₉ ^R 3 one is used in which R .. is a hydrogen atom or / C, -C _C. -alkyl group, R ₂ and R_ are each C ₁ -C _I -alkyl groups, R ₁ , R ₂ and R ₃ together mean a total of 5 to 15 Contain carbon atoms and R ₂ g and R _{39 are} as defined in claim 6. 10. The method according to claim 1, characterized in that at least a compound of the general formula (CH ₀ ) η) -COOR- ² \ / 509 833/0596 used / wherein n _f y and R are as defined in claim 6 and R- is a hydrogen atom, an alkali or alkaline earth atom, an ammonium or alkyl or hydroxyalkylammonium group or a hydroxyalkyl, hydroxyalkoxyalkyl, carboxyalkyl or alkylcarboxyalky group with up to to 12 carbon atoms means. 11. The method according to claim 1, characterized in that there are few stones a compound of one of the general formulas 23 24 -COOR- or (CH ₀ ) 'V-COOR- / 2 η / i used, wherein R _{7 is} a hydrogen atom or a C ₂ -C _g -hydroxyalkyl group and n, R ₂₃ and R _{24 are} as defined in claim 8. 12. The method according to claim 1, characterized in that at least a compound of the general formula Vt t ^S ° x ^NR 28 ^R 29 used, wherein R, y, R ₃₈ and R _{39 are} as defined in claim 6 and χ is 1 or 2 » 13. The method according to claim 1, characterized in that at least a compound of the general formula R ₂ -C-SO _x NR ₂₈ R ₂₉
R ₃ is used, wherein R ₁ , R ₂ , R ₃ , R _2Q and R _{29 are} as defined in claim 9 and χ is 1 or 2. 509833 / G596 2503 & 55 14. The method according to claim 1, characterized in that at least a compound of the general formula ^SO x ^R 1O - Used, wherein R and y are as defined in claim 6 / χ 1 or'2 and R. denotes an alkyl, hydroxyalkyl, carboxyalkyl or alkylcarboxyalkyl group with up to 12 carbon atoms means. ■. 15. The method according to claim 1, characterized in that at least a compound of the general formula R ₃ is used, wherein R., R, and R _{3 are} as defined in claim 9 and R ₁ and χ are as defined in claim 14; 16. The method according to claim 1, characterized in that at least a compound of the general formula Rς-P = O ^R 6 used, wherein R _{4 is} a straight-chain C ₄ -Cg -alkyl group, R, - is a branched-chain C ₃ -C ₅ -alky! group and Rr is a C ^ -Cg -alkyl group or cyclopentyl group, where R ₄ , R ₅ and Rg together have a total of 12 to 18 carbon atoms and at least one of the groups R ₅ and Rg is branched on the carbon atom in a cA ~, β- or ^ "position with respect to the phosphorus atom. 509833/0596 17. The method according to claim 1, characterized in that at least a compound of the general formula ^R 112 "?" ^{0H R} 113 -. used, wherein R _{111 is} a hydrogen atom or a C ₁ -C ₅ -alkyl group and R ₁₁₂ and R _{113 are} each Cp-C ^ -alkyl groups, where a) when R _{111 is} a hydrogen atom, at least one of the groups R ₁₁₀ and R ₁₁ -, one idle I I ^ I I j Group, and b) R ₁₁₁ , R ₁ I ₉ and R ₁₁ -, together a total of 7 to ill I I j £ I I J "; Have 12 carbon atoms. 18. The method according to claim 1, characterized in that at least one compound of the general formula ^(CH 2 ⁾ p (_) ~ ^0H ' is used in which ρ is 0 or an integer from 1 to 5 and R and y are as defined in claim 6, wherein the values for p, R and y are such that the compound is 10-14 carbon contains atoms and if ρ is 1 and y is 2 and one of the two groups R is an isopropyl group in a 2-position in the ring with respect to the OH group and the other group R is a methyl group -er pe means that this methyl group turns into a 1-, 2- _r 3-, 4- or 6-position in the ring with respect to the OH group, 19. The method according to claim 1, characterized in that at least one compound of the general formula ■ ^R 114 '· R ₁₁₅ -C-CH ₂ OH ^R 116 509833/0596. used / in which R ₁₁₄ denotes a hydrogen atom or a Cj-C ^ group, R ₁₁ denotes C and R ₁ -ig taken separately in each case C ₁ -Cg -alkyl groups and taken together denote alkylene groups, which may contain a hydroxyl substituent, and R ₁₁₄ / R ₁₁ C and R _11fi together comprise a total of 6 to 14 carbon atoms. 20. The method according to claim 1, characterized / that at least a compound of the general formula ^{Ri 17} ^ NSN / ^Ri19
R 118 ^{/ Vr} 120 used, wherein R ₁₁ T taken separately a hydrogen atom, a Cj-Cg-alkyl or C_-C means _fi cycloalkyl group, R ₁₁₈ getrenntjgenommen a C ₃ -C ₁ -Alky group, or ^C 3 ~ ^c - _»o ~ alky! ! Cycloalkyl, -Cycloalkyl- or -Cycloalkylalkyl group, where R "" _o on a ck- or ß-carbon atom with respect to 110 of the nitrogen atom is branched and this requirement is also met in the case of cyclic groups if the carbon atom in «Α.- or ß-position to the nitrogen atom is part of the ring, R ₁₁ - and R _{118 taken} together represent a branched-chain alkylene group with 3 to 7 carbon atoms which branch on the d- or ß-carbon atom with respect to the nitrogen atom, where the chain can optionally also contain an ether oxygen atom (-0-), R ₁₁₇ and R ₁₁₈ contain a total of at least 5 carbon atoms, regardless of whether they represent separate groups or taken together, R _11q and R ₁₂ H taken separately are each hydrogen atoms, Ct-Cg-alkyl groups, Cj-Cg-alkylcycloalkyl groups, cycloalkyl groups or cycloalkylalkyl groups, C ₁ -C ₁ -hydroxyalkyl groups, C ₂ -C ₁₀ -carboxyal- 509833/0596 alkyl groups or C ₃ -C ' _Q -alkylcarboxyalkyl groups or, taken together, a straight-chain or branched-chain Co-C _1n "alkylene group, which can optionally be substituted with oxygen or an oxygen-containing group or can contain an ether oxygen atom, and R ₁₁₇ / ^R 118' ^R 119 ^and R ₁₂ together contain a total of 6 to 15 carbon atoms. 21. The method according to claim 1, characterized in that at least a compound of the general formula > 121
^R 118 used, wherein R ₁₁₇ and RJ _{18 are} as defined in claim 20 and R ₁₂ I ^e ^ ⁿ hydrogen atom, a C ₁ -Cg -alkyl group or -alkenyl group, a C '-Cg -cycloalkyl group, a Cj-CQ-hydroxyalkyl ! group, a C ₂ -C .. -carboxyalkyl group or a ^G 3 "- ^c -i _o ~ alkylcarboxyalky! group, a phenyl radical or a C.-C ^ - alkyl, alkoxy, OH, COOH or NO ₂ -substituenten-containing phenyl radical, where, when R _{121 is} a Cg-alkyl group, this is the primary structure. 22. The method according to claim 1, characterized in that at least a compound of the general formula ^R 117
¹¹⁷ ^ NSO ₂ R ₁₂₂ . ^R 118 ' used, wherein R ₁₁₇ and R _{118 are} as defined in claim 20 and R _{122 is} a C 1 -C 6 alkyl group and C 1 -C 6 cycloalkyl group, where, when R ^ _{22 is} a C ₅ or C 8 alkyl group, this primary structure is. 50 983 3/0596 23. The method according to claim 1, characterized in that at least a compound of the general formula used, in which X is an OH group, the two OH substituents being bonded to different carbon atoms and at least one is in the 2- or 3-position. 24. The method according to claim 1 to 23, characterized in that the taste modifier in an amount of 0.1 to 100 ppm, based on the total preparation or the total substance, clogs. 25. The method according to claim 24, characterized in that the Flavor modifier is added in an amount of 0.1 to 10 ppm. 509833/0596