CH632906A5 - Use of bifunctional N,S-compounds as flavourings - Google Patents

Description

The invention relates to the use of bifunctional N, S compounds as flavorings. These N, S compounds represent compounds of the formula in which R 1 and R 2 are C 1 -C 4 -alkyl, A is an optionally branched alkylene group, R is hydrogen, methyl, ethyl, form

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myl, acetyl, propionyl or the rest -A-N ° der

2nd

-S-A-NCT represent.

2nd

CI_3-alkyl stands for methyl, ethyl, propyl, isopropyl. Methyl is preferred.

A represents an alkylene group such as methylene, ethylene, propylene or butylene. Ethylene and propylene are preferred. One or more of the H atoms of the alkylene chain can be substituted, in particular substituted by a methyl group.

The preferred R radicals are hydrogen or methyl.

Although a large number of the compounds covered by the formula I are known, it cannot be inferred from the corresponding literature that such compounds I have any organoleptic properties.

As has now surprisingly been found, the compounds of the formula I are notable for special flavor properties, on the basis of which they are particularly suitable as flavorings. The range of flavors is very wide. Fruity, spicy (e.g. mustard-like), vegetable notes, e.g. for leeks, celery, cauliflower, chives, onions, garlic, asparagus, rhubarb, tomato etc., mushroom-like, as well as cheese and meat notes. Of particular interest are the roasted, meat and fish dishes, e.g. the notes of roast roast, poultry,

Fish, especially tuna, sardines, anchovies. There are also interesting egg and potato notes.

Accordingly, the compounds I can be used, for example, for flavoring products, such as foods, luxury foods and beverages, the compounds I preferably not being used alone, but in the form of compositions with other flavors. Such flavoring compositions containing compounds of the formula I are expediently prepared in a manner known per se, that is to say by adding the compounds I to known flavoring compositions or mixing compounds I with natural or synthetic compounds or mixtures suitable as a component of flavoring compositions.

The flavor compositions should contain the compounds I in practically pure form or in the form of mixtures.

Practically pure should be understood in particular to mean that the compounds I are free of the accompanying substances, as are present in addition to compounds I in mixtures originating from any natural source; in other words, the mixtures of compounds of formula I derived from any natural source should be excluded. Practically pure compounds I in the sense of the present invention are to be understood in particular as synthetically produced such compounds.

As flavorings, the compounds I can be used, for example, to produce or improve, reinforce, increase or modify fruit, meat, vegetable, cheese, mushroom-like, spicy or roasted notes in foods (such as meat, fish, seafood products, meat substitute products, sauces, Bouillons, soups, e.g. dry soups, vegetables, such as various types of cabbage, legumes, leeks, onions, seasonings, e.g. mustard, ketchup, soy sauce, in flavor enhancers, snack foods, roasted products such as nut products, coffee or cocoa, milk products such as cheese, curd cheese, yoghurt etc.), in luxury foods (tobacco, chocolate, crackers, etc.) and beverages (lemonades, etc.).

The pronounced taste qualities enable the use in low concentrations. A suitable dosage ranges from about 0.001-100 ppm, preferably from about 0.1-10 ppm in the finished product, i.e. the flavored food, luxury food or drink.

The compounds I can be mixed in a conventional manner with the constituents used for flavoring compositions, preferably together with other flavoring constituents and / or adsorbent and carrier substances and / or diluents, inclusion (encapsulation) substances, emulsifiers, stabilizing agents, etc. Flavors can be added. Such aromas are understood to mean flavoring compositions which can be diluted in a manner known per se or which can be distributed in edible materials. They can be converted into the usual forms of use, such as solutions, pastes or powders, using methods known per se. The products can be spray dried, vacuum dried or lyophilized. The formulation of such artificial aromas and the aromatization of the products can be carried out in a conventional manner (cf. J. Merory; Food favourings, composition, ma

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632 906

manufacture and use; Avi Pubi. Co. Inc. Westport (1968), or A.M. Burger; the natural and artificial flavors; A. Hüthig Verlag Heidelberg 1968).

Suitable carrier materials, thickeners, taste improvers, spices and auxiliary ingredients, etc., which are suitable for the production of such customary forms of use are, for example:

Exudates, guar gum, tara gum, pectin, xanthan, modified starches and celluloses, gum arabic, tragacanth, salts or brewer's yeast, alginates, carrageenan or similar absorbents; flavoring ingredients, maltol, spice oleoresins, smoke flavors; Cloves, meat extracts, Maillard products, sodium citrate; Monosodium glutamate, disodium inosine 5'-monophosphate

(IMP), disodium guanosine 5-phosphate (GMP); Milk and cheese powder; or special flavors, diluents such as water, ethanol, propylene glycol, glycerin, benzyl alcohol, citric acid esters, fatty acid esters, edible oils, stabilizing agents such as antioxidants, e.g. BHT, BHA etc., buffer compounds such as e.g. B. phosphates, citrates etc.

The concentration of the compounds I in the aroma compositions can vary within wide ranges, for example between about 1 ppm and 100%. A preferred range is that between about 10 ppm and 10%.

The table below gives an indication of suitable flavoring substance concentrations in different application forms:

Application form generally preferred

Compositions in liquid form, e.g. Solutions [in water,

Alcohols, (ethanol, glycerin, benzyl alcohol, propylene glycol, etc.)], esters, e.g. Citric acid esters, fatty acid esters 1 ppm-10%, 10ppm-10% o pastes 10 ppm- 50% o 100ppm-10% o spray-dried powder 50ppm-100% o 300ppm-30% o lyophilized vacuum-dried powder 50 ppm- 100% o 300 ppm- 30% o adsorbed powders (adsorbates) 50ppm-100% o 300ppm-30% o food extender 50 ppb -100 ppm 300 ppb -30 ppm structured proteins for meat substitutes 50 ppb -100 ppm 300 ppb -30 ppm dip sauces 50 ppb -100 ppm 300 ppb-30 ppm cocktail sauces 50 ppb -100 ppm 300 ppb -30 ppm meat sauces 100 ppb -100 ppm 200 ppb -20 ppm mashed potatoes 50 ppb -100 ppm 300 ppb -30 ppm soups 10 ppb - 50 ppm 100 ppb - 10 ppm canned meat 10 ppb - 50 ppm 100 ppb-10 ppm ready meals, e.g. Meat dishes 10 ppb - 50 ppm 100 ppb -10 ppm meat extracts and Maillard products 10 ppm- 50% o 100ppm-10% o seasonings (e.g. aromatics) 10 ppm- 50% o 100ppm-10% o cheese powder and cheese extender 50 ppb -100 ppm 300 ppb -30 ppm vegetable powder and extenders 50 ppb -100 ppm 300 ppb -30 ppm

In special cases, the compounds I can also be added alone to the products to be flavored. In this case, special attention must be paid to an even distribution in the product to be flavored when adding.

Particularly interesting compounds due to their aroma properties are:

(CH3) 2N (CH2) 3SH

according to sardine, tuna (CH3) 2N (CH2) 3SCH3 potato-like, fatty (CH3) 2N (CH2) 3SCOCH3

meaty, tuna, especially roasted (CH3) 2N (CH2) 2SH

meaty, light fish note, pungent (CH3) 2N (CH2) 2SCH3

(CH3) 2NCH (CH3) CH2SH 40 after beef, interesting roasted notes (CH3) 2NCH (CH3) CH2SCOCH3

after roast, roasted note (C2H5) 2N (CH2) 4SH after fried fish 45 (CH3) 2NCH2CH (CH3) SCH3 after cheese, spicy (CH3) 2NCH (CH3) CH2SCH3 after sauerkraut, cabbage.

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example 1

A dip mix for sauce can be obtained as follows: 40.0 g of a mixture consisting of

Parts by weight

55 * sour cream, spray-dried after green tomatoes, potatoes

(e.g. SAA-Creme-H)

89.4

(C2H5) 2N (CH2) 2SH

Sodium glutamate

7.29

meaty, potato-like, interesting roasted notes, spicy

Hydrolyzed vegetable protein

(i-Prop) 2N (CH2) 2SH

(e.g. HPP, type RF-B, oil coated)

1.66

after meat pie

60 citric acid

0.17

(i-Prop) 2N (CH2) 2SCOCH3

Pepper flavor

0.17

meaty, like sardine

Marjoram flavor

0.03

(CH3) 2N (CH2) 2SS (CH2) 2N (CH3) 2

Thyme flavor

0.03

after vegetables, cabbage

Turmeric aroma

0.26

(CH3) 2N (CH2) 3S (CH2) 3N (CH3) 2

65 salt

0.66

greasy, interesting roasted notes, after roast

Mustard powder

0.33

(CH3) 2N (CH2) 3SS (CH2) 3N (CH3) 2

100.00

for potatoes, fish, amine-like

* spray-dried sour cream base with vegetable fat.

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are mixed and dissolved with 50 ml of water while stirring.

The taste of this dip sauce is weak and uncharacteristic. The addition of 3-5 ppm of 2-di-isopropylaminoethyl mercaptan gives this dip sauce a pleasant, meat-like note that harmonises well with the existing spice note.

Example 2

A cocktail sauce flavor can have the composition A or B:

A B

Parts by weight

Levulinic acid

10th

10th

Raspberry ketone

10th

10th

Dimethyl disulfide

(1% in propylene glycol)

1

1

Dimethyl sulfide

(1% in propylene glycol)

2nd

2nd

Piperidine

5

5

Thiolactic acid

5

5

3-acetylpyridine

10th

10th

Terpinen-4-ol

3rd

3rd

Trimethylamine

(25% in propylene glycol)

40

40

Propylene glycol

914

913.5

S-acetyl-2-diisopropylamino-ethyl

mercaptan (1% in propylene glycol)

0.5

1000 1000

With a dosage of 200 g / 1001 cocktail sauce, the smell and taste of the composition A are bland.

The addition of S-acetyl-2-diisopropylamino-ethyl mercaptan greatly improves the taste by creating a note that is strongly reminiscent of sardines (composition B).

A similar effect is achieved if, instead of S-acetyl-2-diisopropylamino-ethyl mercaptan, 0.5 part by weight of a 1% propylene glycol solution of 4-diethylamino-butyl-mercaptan is used.

Example 3

A cocktail sauce flavor can have the composition A or B:

A B

Parts by weight

Levulinic acid

10th

10th

Raspberry ketone

10th

10th

Dimethyl disulfide

(1% in propylene glycol)

1

1

Dimethyl sulfide

(1% in propylene glycol)

2nd

2nd

Piperidine

5

5

Thiolactic acid

5

5

3-acetylpyridine

10th

10th

Terpinen-4-ol

3rd

3rd

Trimethylamine

(25% in propylene glycol)

40

40

Propylene glycol

914

913.5

2-dimethylaminoethyl mercaptan

(1% in propylene glycol)

0.5

1000 1000

With a dosage of 200 g / 1001 cocktail sauce, the smell and taste of the composition A are bland.

The addition of 2-dimethylamino-ethylmercap-tan greatly improves the taste, and the note that now appears is reminiscent of anchovies (composition B).

Example 4

A cocktail sauce flavor can have the composition A or B:

A B

Parts by weight

Levulinic acid

10th

10th

Raspberry ketone

10th

10th

Dimethyl disulfide

(1% in propylene glycol)

1

1

Dimethyl sulfide

(1% in propylene glycol)

2nd

2nd

Piperidine

5

5

Thiolactic acid

5

5

3-acetylpyridine

10th

10th

Terpinen-4-ol

3rd

3rd

Trimethylamine

(25% in propylene glycol)

40

40

Propylene glycol

914

913.5

3-dimethylamino-propyl mercaptan

(1% in propylene glycol)

0.5

1000 1000

With a dosage of 200 g / 1001 cocktail sauce, the smell and taste of the composition are bland.

The addition of 3-dimethylamino-propyl-mercaptan changes the taste in an advantageous manner by adding a note reminiscent of sardines and tuna (composition B).

Instead of 3-dimethylamino-propyl mercaptan, 3-dimethylaminopropyl disulfide can be used in the above aroma.

Example 5

A brown meat sauce can be obtained as follows: 20 g of a mixture consisting of

Parts by weight

Dried meat extract, finely ground 18

Vegetable fat 15 Roasted onion aroma 0.4 Salt 5.6

Sodium glutamate 16 hydrolyzed vegetable protein (e.g. HPP, type 3 Hl, oil coated or type

RF-B, oil coated) 20 caramel powder 1 coriander flavor 0.3 marjoram flavor 0.1 laurel flavor 0.12 citric acid 0.28

Modified potato starch 23.20

100.00

are stirred into 1 liter of cold water and boiled with constant stirring. After a cooking time of 3 minutes, the smell and taste of this sauce are weak and uncharacteristic.

After adding 3-5 ppm S-acetyl-3-dimethylamino-propyl mercaptan, an excellent roasted meat note is found.

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Example 6

A potato flavor composition can have the composition A or B:

A B parts by weight

Valeric acid 0.3 0.3

Vanillin 1.2 1.2

Ethyl butyrate 2.5 2.5

Lactic acid 2.5 2.5

Butyric acid 2.5 2.5

Diacetyl 3.0 3.0

Methional 60.0 40.0

(3-dimethylaminopropyl) -

methyl sulfide 20.0

Ethyl alcohol 928.0 928.0

1000.0 1000.0

A comparison of A and B shows that composition A falls sharply.

A partial improvement of methional with (3-dimethylaminopropyl) methyl sulfide improves the taste. Aroma B has a more pronounced potato note that is reminiscent of chips.

Example 7

A cheese flavor can have a composition A or B:

A B

Parts by weight

Lactic acid

10th

10th

Butyric acid ethyl ester

30th

30th

Ammonium isovalerate

30th

30th

i-valeric acid

50

50

Caproic acid

60

60

Butyric acid

120

120

(2-dimethylaminoethyl) -

methyl sulfide

5

Propylene glycol

700

695

1000

1000

A comparison of A and B shows that the conventional composition A drops sharply.

The addition of (2-dimethylaminoethyl) methyl sulfide has advantageously enhanced the cheese aroma in composition B; the composition is reminiscent of cheddar cheese.

Example 8

A clear meat soup can be prepared as follows: 20.0 g of a mixture consisting of

Parts by weight

Salt 50.15

Sodium glutamate 20.0

Caramel powder 0.2

Muscat aroma 0.05

Clove aroma 0.05

Pepper flavor 0.05 hydrolyzed vegetable protein (e.g.

H VP, type 3 Hl and HVP, type RF-B) 11.5

Vegetable fat (mp. 40 ° C) 17.0

Onion powder 1.0

100.0

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are poured into 1 liter of hot water.

The taste of this soup is weak and uncharacteristic. The addition of 3-5 ppm of 2-diethylamino-ethyl mercaptan advantageously enhances the existing meat taste, and a pleasant roasted meat note now appears that harmonises well with the meat taste.

Example 9

Dried imitation bacon bits can be obtained as follows:

Parts by weight

Colored textured soy protein

(Miratex 405) 750 g

Palm kernel fat (mp 32-34 ° C) 160 g

Salt 50 g

Na glutamate 10 g

Vegetable protein hydrolyzate 25 g

Pepper flavor 2.7 g

Onion flavor 0.2 g

Garlic flavor 0.1 g

Smoke flavor (smoke flavor) 2 g

1000 g

The ingredients - with the exception of the soy protein - are mixed well in the melted palm kernel fat in a mixer and dried in a rotary dryer (tumbler) together with the soy product at 35 ° C. The granular mass hardens by cooling. This can e.g. used as an extender or substitute for bacon in omelets, beans, soups and sauces, sandwiches and salads, etc.

However, the product has a somewhat bland, non-specific taste. By adding 2-5 ppm of 2-di-ethylamino-ethyl mercaptan and / or 2-5 ppm of 2-diisopropylamino-ethyl mercaptan to the fat suspension, the imitation bacon cubes produced in this way acquire a meaty, bacon-like, pleasant character.

Example 10

An all purpose seasoning pow-der can be obtained as follows:

Parts by weight

Table salt

354 g

Na glutamate

200 g

Vegetable protein hydrolyzate

200 g

Cornstarch

100 g

Palm kernel fat

Mp 32-34 ° C

50 g

Onion powder

50 g

Yeast autolysate

25 g

Turmeric powder

13 g

1% propylene glycol solution of 2- (di-

methylamino) propyl mercaptan

8g

1000 g

The turmeric powder is emulsified in palm kernel fat and then mixed with the other ingredients. The powder obtained is used to season food both in the kitchen and at the dining table.

By omitting 2- (dimethylamino) propyl mercaptan, an uncharacteristic seasoning powder is obtained which lacks the desired meaty note.

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Example 11

A straight cheese powder can be obtained as follows:

Parts by weight

Parts by weight

Cheese powder

500 g

Pre-cooked corn starch

50 g

Buttermilk powder

150 g

Maltodextrin

285 g

Table salt

4.9 g

citric acid

5 g

Na citrate

5 g

(2-dimethylaminopropyl) methyl sulfide

[1% in propylene glycol]

0.1g

1000 g

The ingredients are mixed well, resulting in a cheese-like product that is suitable for seasoning spaghetti, pizza, soups, pastries, dip sauces, etc.

If the (2-dimethylaminopropyl) methyl sulfide is not added, the product will appear too empty and bland.

Example 12

A ready seasoned hamburger helper mix with textured soy protein can be obtained as follows:

Parts by weight

Textured soy protein (Miratex 210)

and palm kernel fat (mp. 32-34 ° C) are mixed in a mixer dryer at 35 ° C and mixed with:

700 g 70 g

Cooking salt 5 Na-glutamate vegetable protein hydrolyzate Pepper flavor Onion flavor Garlic flavor 10 1% propylene glycol solution of 3-dimethylaminopropyl sulfide By adding

Egg powder and

15 dried onion flakes you get a durable powder, which with

Minced beef and 20 water mixed and fried in portions gives a pleasant smell of roast hamburgers.

30 g 10 g 16 g 2.3 g 0.5 g 0.2 g

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70 g

100 g 1000 g

2400 g

1600 g

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If the 3-dimethylaminopropyl sulfide is not added, the hamburgers taste weak and bland. On the other hand, if it is replaced by an equal amount of S-acetyl-3-dimethylamino-propyl mercaptan, an excellent roasted meat note is again achieved.

If they are not described in the literature, the compounds of the formula I can be prepared in a manner known per se, as summarized in the table below:

Method*

Products (Formula I)

Educts

Solvents e.g.

Temperature range e.g.

B

N, N-dialkylamino alkyl mercaptan

N, N-dialkylamino alkyl sulfide

S-acyl-dialkylamino-alkyl-mercaptan

(N, N-Dialkylamino-alkyl) disulfide

S-acyl-dialkylamino-alkyl-mercaptan 2)

Dialkylamino alkyl halide 1)

Dialkylamino alkyl halide 1)

Dialkylamino alkyl mercaptan

D

Dialkylamino alkyl halide 1)

(Contact educt with solvent, e.g. a few minutes to several days) alkyl mercaptan

Thio-alkane carboxylic acid or salt (e.g. alkali metal salt). Oxidizing agents, e.g. J2.02, H202, org. or anorg. Peroxide alkali metal hydrogen sulfide

(N, N-Dialkylamino-alkyl) sulfide * see the examples below.

1) chloride, bromide, iodide.

2) expediently containing easily removable acyl group, such as formyl, acetyl, propionyl, benzoyl.

Methanol, ethanol, propanol, water

Base / org.LM, esp. 2-phase system NaOH / benzene, KOH / benzene or NaOH / ether, KOH / ether org., Esp. Apron. Solvents, e.g. Chloroform, H20 NaOH / ether, such as C

NaOH / benzene, such as C

0-100 ° C, especially 20-65 ° C

0-100 ° C, especially 20-60 ° C

0-100 ° C, especially 20-60 ° C

-80-100 ° C, esp. 10-30 ° C

0-100 ° C, especially 20-60 ° C

Example 1 (Method A) 100 g of 3-dimethylamino-l-propyl chloride hydrochloride are dissolved in 1.2 liters of chloroform and mixed with 192 g of triethylamine. 54 ml of thioacetic acid are added dropwise and the mixture is kept at reflux temperature for 18 hours. The cooled reaction solution is washed three times with 500 ml in NaOH and once with 500 ml of water. The aqueous phases are shaken out with CHC13 and the combined CHC13 phases

60 dries, concentrated and distilled at 86-89 ° C / 10 mm Hg. In this way, 91.3 g (89.5%) of pure S-acetyl-3-dimethylamino-propyl mercaptan are obtained.

According to the same method are obtained:

65 S-acetyl-3-dimethylamino-propyl mercaptan: S-acetyl-2-diisopropylamino-ethyl mercaptan:

38-44 ° C / 0.04 mm Hg 102-108 ° C / 10 mm Hg

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S-acetyl-2-dimethylamino

propyl-mercaptan: 84-87 ° Cj 11 mm Hg

Example 2 (Method B) 86.4 g of S-acetyl-3-dimethylarninopropyl mercaptan are kept in 900 ml of methanol at reflux temperature for 15 hours. The methyl alcohol is then distilled off and the residue is distilled at 150-155 ° C. under normal pressure. In this way, 44.2 g (69% yield) of pure 3-dimethylaminopropyl mercaptan, b.p. 10 42 ° C./10 mm Hg.

The following method is used to obtain: 2-diisopropylaminoethyl mercaptan 72-74 ° C / 10 mm Hg 2-dimethylamino propyl mercaptan 125-145 ° C

2-dimethylaminoethyl mercaptan 124-128 ° C 15

2-diethylamino-ethyl mercaptan 160 QC

Example 3 (Method C)

10 g of l-dimethylamino-propyl-2-chloride hydrochloride, 100 ml of 2N aqueous sodium hydroxide solution, 20 100 ml of benzene and 0.8 g of benzyl-triethylammonium chloride are placed in a flask; methyl mercaptan (about 20 g) is introduced with stirring at room temperature for 40 minutes. The mixture is then held at the reflux temperature for four hours. The benzene phase is concentrated and distilled; at 165 to 168 ° C., it gives 2.4 g (29% yield) of a mixture of [l-dimethylamino-propyl- (2)] - methyl sulfide and 2-dimethylaminopropyl-methyl sulfide in a ratio of 15 to 85. The two products can be separated 30 by preparative gas or column chromatography.

The following method is used to obtain: (3-dimethylaminopropyl) methyl sulfide

90-100 ° C / 25 mm Hg (2-dimethylaminoethyl) methyl sulfide 130-133 ° C

Example 4 (Method D)

10 g of 3- (dimethylamino) propyl chloride hydrochloride, 100 ml of 2N sodium hydroxide solution, 100 ml of benzene, 0.5 g of benzyltriethylammonium chloride hydrochloride and 6.7 g of NaHSH20 (70%) are placed in a flask for 24 hours at reflux temperature held. The aqueous phase is then extracted three times with 50 ml ether; the combined organic phases are washed with water, concentrated and fractionally distilled at 75 to 85 ° C / 0.025 mm Hg. 1.35 g of 3-dimethylaminopropyl sulfide (21% yield) result as a clear, colorless liquid.

Example 5 (Method E)

Iodine is added in portions to a mixture of 4 g of 3-dimethylamino-propyl mercaptan in 60 ml of ether and 30 ml of 2N sodium hydroxide solution until the reaction solution is no longer decolorized (about 4.2 g of iodine). After stirring for one hour, the ether phase is dried with MgS04, concentrated and fractionally distilled at 95-100 ° C / 0.025 mm Hg. The result is 2.7 g (68%) of 3-dimethylaminopropyl disulfide as a clear, colorless liquid.

The same method is used to obtain: 2-dimethylaminoethyl disulfide 130-132 3C / 10 mm Hg

Claims (3)

632 906 2. Use according to claim 1, characterized in that Rj and R2 represent methyl, A is ethylene or propylene and R is hydrogen or methyl. 2nd in practically pure form or in the form of mixtures as flavorings. 2nd Represent -S-A-N, 2nd PATENT CLAIMS 1. Use of compounds of the formula X N-A-S-R I / R- where Rj and R2 are C 1-4 alkyl, A is an optionally branched alkylene group, R is hydrogen, methyl, ethyl, form myl, acetyl, propionyl or the rest-A-N ^ "" 1 or 3. Use according to claim 1 or 2, characterized in that Rj and R2 represent methyl, A propylene and R are hydrogen.