GB1590147A

GB1590147A - Flavouring compositions

Info

Publication number: GB1590147A
Application number: GB33146/77A
Authority: GB
Original assignee: L Givaudan and Co SA
Current assignee: Givaudan SA
Priority date: 1976-08-09
Filing date: 1977-08-08
Publication date: 1981-05-28
Also published as: NL7708541A; DE2735459A1; GB1590148A; FR2392610A1; CH632906A5; JPS5329945A

Abstract

The compounds of the formula <IMAGE> in which R1 and R2 are C1-3-alkyl, A is an optionally branched alkylene group, R is hydrogen, methyl, ethyl, formyl, acetyl, propionyl or the radical <IMAGE> or <IMAGE>, are flavourings. They can be used for flavouring general and luxury foodstuffs and beverages.

Description

(54) FLAVOURING COMPOSITIONS (71) We, L. GIVAUDAN & CIE, Société Anonyme, a Swiss Company of Vernier Genève, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to. be particularly described in and by the following statement: The present invention relates to flavouring compositions. More particularly, the invention is concerned with flavouring compositions, a process for the manufacture thereof and a method of imparting a flavour to materials using said compositions or the essential flavour-imparting ingredients thereof.

The flavouring compositions provided by the present invention contain a compound of the general formula

wherein R1 and R2 each represent a C13-alkyl group, A represents an alkylene group which may be branched and R represents a hydrogen atom or the methyl, ethyl, formyl, acetyl or propionyl group or a group of the formula

in which A, R1 and R2 have the significance given earlier.

The C1~3-alkyl group aforesaid is the methyl, ethyl, propyl or isopropyl group. The methyl group is the preferred C1~3-alkyl group. The symbol A represents an alkylene group such as the methylene, ethylene, propylene or butylene group. The ethylene and propylene groups are the preferred alkylene groups. One or more of the hydrogen atoms of the alkylene chain can be substituted, in particular by methyl. R preferably represents a hydrogen atom or the methyl group.

Although a large number of the compounds of formula I are known, there is no disclosure in the corresponding literature sources that any of said compounds have any organoleptic properties.

It has now surprisingly been found in accordance with the present invention that the compounds of formula I possess particular flavouring properties and are, accordingly, very well suited as flavour-imparting ingredients in flavouring compositions. The flavouring spectrum is very broad. The compounds of formula I possess fruity, spicy (e.g. mustard-like), vegetable-like (e.g. leek, celery, cauliflower, chive, onion, garlic, asparagus, rhubarb, tomato etc) and mushroom-like notes as well as cheese and meat notes. Of particular interest are the roast, meat and fish notes; for example, the notes of roast meat, poultry and fish, in particular tuna fish, sardines and anchovies. However, interesting egg and potato notes are also present.

The compounds of formula I can accordingly be used, for example, for the aromatisation of products such as foodstuffs, luxury goods and drinks, said compounds preferably not being used alone but rather in the form of compositions containing other flavouring substances.

The present invention is based on the finding mentioned earlier and is concerned in one aspect with a flavouring composition which contains as an essential flavour-imparting ingredient a compound of formula I hereinbefore in virtually pure form or in the form of mixtures (with the exception of mixtures which contain compounds of formula I and which originate from natural sources), together with at least one other flavour-imparting ingredient and/or a carrier or diluent.

The invention is also concerned in another aspect with a process for the manufacture of the flavouring compositions aforesaid, which process comprises adding a compound of formula I in virtually pure form or in the form of mixtures (with the exception of mixtures which contain compounds of formula I and which originate from natural sources) to known flavouring compositions or mixing a compound of formula I in virtually pure form or in the form of mixtures (with the exception of mixtures which contain compounds of formula I and which originate from natural sources) with natural or synthetic compounds or mixtures thereof suitable as constituents of flavouring compositions.

In yet another aspect, the invention is concerned with a method of imparting a flavour to materials, which method comprises applying to said materials or incorporating therein a flavour-imparting amount of a compound of formula I in virtually pure form or in the form of mixtures (with the exception of mixtures which contain compounds of formula I and which originate from natural sources) or of a flavouring composition as hereinbefore defined.

As already mentioned, the flavouring compositions provided by the present invention should contain the compounds of formula I in virtually pure form or in the form of mixtures, with the exception of mixtures which contain compounds of formula I and which originate from any natural sources.

The expression "virtually pure" is used herein to mean, in particular, that the compounds of formula I are free from the impurities which are present in addition to the compounds of formula I in mixtures originating from any natural sources. As virtually pure compounds I in the scope of the present invention, there are to be understood, in particular, those compounds which are synthetically prepared.

The compounds of formula I can be used as flavouring substances, for example, for the production of improvement, intensification, enhancement or modification of fruit, meat, vegetable, cheese, mushroom-like, spicy or roast notes in foodstuffs (e.g. meat, fish, seafood products, meat-substitute products, sauces, broths, soups such as dry soups, vegetables such as various type of cabbage, legumes, leaks and onions, spicing agents such as mustard, ketchup and soya sauce, flavour strengtheners, snack food, roasted products such as nut products, coffee or cocoa, dairy products such as cheese, quark and yoghurt etc), in luxury goods (e.g. tobacco, chocolate, crackers etc) and drinks (e.g. lemonades etc).

The pronounced flavour qualities of the compounds of formula I enable them to be used in low concentrations. A suitable range is ca 0.001 ppm - 100 ppm, preferably ca 0.1 ppm 10 ppm, in the finished product (i.e. the flavoured foodstuff, luxury goods or drink).

The compounds of formula I can be mixed with the constituent used for flavouring compositions, preferably together with other flavour-imparting ingredients and/or adsorption and carrier substances and/or diluents, enveloping (encapsulating) substances, emulsifiers, stabilising agents etc, or added to such flavours in the customary manner.

Among the flavours contemplated according to the present invention there are to be understood flavouring compositions which can be diluted or dispersed in edible materials in a manner known per se. They can be converted into the customary forms of use such as solutions, pastes or powders, according to methods known per se. The products can be spray-dried, vacuum dried or lyophilised. The formulation of these synthetic flavours and the flavouring of the products can also be carried out in a manner known per se [see J.

Merory; Food flavourings, composition, manufacture and use; Avi Publ. Co. Inc. Westport (1968), or A. M. Burger; die natürlichen and kiinstlichen Aromen; A. Hiithig, Verlag Heidelberg 1968].

Examples of suitable carriers, thickeners, flavour-improvers, spices, auxiliary ingredients and the like which can be used in the production of such customary forms of use are: Exudates, guar gum, tara gum, pectin, xanthane, modified starches and cellulose, gum arabic, tragacanth, salts or brewers' yeast, alginates, carrageens or similar absorbants; flavour-imparting ingredients, maltol, spice oil resins, smoke flavours; cloves, meat extract, Maillard products, sodium citrate; monosodium glutamate, disodium inosine-5'monophosphate (IMP), disodium guanosine-5-phosphate (GMP); milk and cheese powder; special flavour substances, diluents such as water, ethanol, propyleneglycol, glycerine, benzyl alcohol, citric acid esters, fatty acid esters, olive oil; stabilising agents such as antioxidants (e.g. butylated hydroxytoluene, butylated hydroxyanisole etc), buffer substances such as, for example, phosphates, citrates etc.

The concentration of the compounds of formula I in the flavour compositions can vary within a wide range (e.g. between about 1 ppm and 100"/or). A preferred range is between 10 ppm and 10 /oo.

The following Table illustrates suitable concentrations of flavour substances in various forms of application: TABLE Form of use General Preferred Compositions in liquid form e.g.

Solutions [in water, alcohols (ethanol, glycerine, benzyl alcohol, propyleneglycol etc), esters (e.g. citric acid esters, fatty acid esters)] 1 ppm-100/oo 10 ppm-10 /oo Pastes 10 ppm-50 /oo 100 ppm-100/oo Spray-dried powders 50 ppm-100 /oo 300 ppm-30 /oo Lyophilised vacuum dried powders 50 ppm-1000/oo 300 ppm-300/oo Adsorbed powders (adsorbates) 50 ppm-1000/oo 300 ppm-30 /oo Diluting agent for foodstuffs 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 Potato stock 50 ppb-100 ppm 300 ppb-30 ppm Soups 10 ppb-50 ppm 100 ppb-10 ppm Meat preservatives 10 ppb-50 ppm 100 ppb-10 ppm Ready-made dishes (e.g. meat dishes) 10 ppb-50 ppm 100 ppb-10 ppm Meat extracts and Maillard products 10 ppm-50 /oo 100 ppm-10 /oo Spice agent (e.g. Aromat) 10 ppm-50 /oo 100 ppm-10 /oo Cheese powder and cheese extender 50 ppm-100 ppm 300 ppb-30 ppm Vegetable powder and extender 50 ppb-100 ppm 300 ppb-30 ppm In the Table, "ppb" is parts per billion (billion = one thousand million).

In special cases, the compounds of formula I can also be added alone to the products to be flavoured. In this case particular care must be taken during the addition to achieve a uniform dispersion of such a compound in the product being aromatised.

The following Table lists compounds of formula I which are of particular interest having regard their aroma properties: TABLE Compound Aroma (CH3)2N(CH2)3SH after sardines, tuna fish (CH3)2N(CH2)3SCH3 potato-like, fatty (CH3)2N(CH2)3SCOCH3 meat-like, tuna fish, roast note in particular (CH3)2N(CH2)2SH meat-like, slight fish note, penetrating (CH3)2N(CH2)2SCH3 after green tomatoes, potatoes (C2H5)2N(CH2)2SH meat-like, potato-like, interesting roast note, spicy (i-Prop)2N(CH2)2SH after meat pastry (i-Prop)2N(CH2)2SCOCH3 meat-like, after sardines (CH3)2N(CH2)2SS(CH2)2N(CH3)2 after vegetables, cabbage (CH3)2N(CH2)3S(CH2)3N(CH3)2 fatty, interesting roast note, after roast meat (CH3)2N(CH2)3SS(CH2)3N(CH3)2 after potatoes, fish, amine-like (CH3)2NCH(CH3)CH2SH after beef, interesting roast note (CH3)2NCH(CH3)CH2SCOCH3 after roast meat, roast note (C2H5)2N(CH2)4SH after fried fish (CH3)2NCH2CH(CH3)SCH3 after cheese, strong (CH3)2NCH(CH3)CH2SCH3 after sauerkraut, cabbage The following Examples illustrate the present invention: Example 1 A dip mix for sauce can be prepared as follows: 40.0 g of a mixture consisting of Parts by Weight *Sour cream, spray dried (e.g.

SAA-creme-H) 89.4 Sodium glutamate 7.29 Hydrolysed vegetable protein (e.g.

HPP, Type RF-B, oil-coated) 1.66 Citric acid 0.17 Pepper aroma 0.17 Marjoram aroma 0.03 Thyme aroma 0.03 Curcuma aroma 0.26 Salt 0.66 Mustard Powder 0.33 100.00 are mixed and dissolved with 50 ml of water while stirring.

The flavour of this dip sauce is weak and uncharacteristic. By adding 3-5 ppm of 2-diisopropylaminoethylmercaptan, the resulting dip sauce is given a pleasant, meat-like note which harmonises well with the existing spice note.

*spray-dried sour cream base with vegetable fat.

Example 2 A cocktail sauce aroma can have the composition A or B: A B Parts by weight Levulinic acid 10 10 Raspberry ketone 10 10 Dimethyl disulphide (1% in propyleneglycol 1 1 Dimethyl sulphide (1% in propyleneglycol) 2 2 Piperidine 5 5 Thiolactic acid 5 5 3-Acetylpyridine 10 10 Terpinen-4-ol 3 3 Trimethylamine (25% in propyleneglycol 40 40 Propyleneglycol 914 913.5 S-Acetyl-2-diisopropylamino ethylmercaptan (1% in propylene- 0.5 glycol) 1000 1000 At an amount of 200 g/100 litres of cocktail sauce, the odour and flavour of composition A are insipid.

By adding S-acetyl-2-diisopropylaminoethylmercaptan, the flavour is greatly improved in that a note emerges which is strongly reminiscent of sardines (Composition B).

A similar effect is achieved by using 0.5 parts by weight of a 1% propyleneglycol solution of 4-diethylaminobutylmercaptan in place of S-acetyl-2-diisopropylaminomethylmercaptan.

Example 3 A cocktail sauce aroma can have the composition A or B: A B Parts by weight Levulinic acid 10 10 Raspberry ketone 10 10 Dimethyl disulphide (1% in propyleneglycol) 1 1 Dimethyl sulphide (1% in propyleneglycol) 2 2 Piperidine 5 5 Thiolactic acid 5 5 3-Acetylpyridine 10 10 Terpinen-4-ol 3 3 Trimethylamine (25% in propyleneglycol) 40 40 Propyleneglycol 914 913.5 2-Dimethylaminomethylmercaptan (1% in propyleneglycol) 0.5 1000 1000 At an amount of 200 g/100 litres of cocktail sauce, the odour and flavour of composition A are insipid.

By adding 2-dimethylaminomethylmercaptan the flavour is greatly improved, the note which now emerges being reminiscent of anchovies (Composition B).

Example 4 A cocktail sauce aroma can have the composition A or B: A B Parts by weight Levulinic acid 10 10 Raspberry ketone 10 10 Dimethyl disulphide (1% in propyleneglycol) 1 1 Dimethyl sulphide (1% in propyleneglycol) 2 2 Piperidine 5 5 Thiolactic acid 5 5 3-Acetylpyridine 10 10 Terpinen-4-ol 3 3 Trimethylamine (25% in propyleneglycol 40 40 Propyleneglycol 914 913.5 3-Dimethylaminopropylmercaptan (1% in propyleneglycol) 0.5 1000 1000 At an amount of 200 g/100 litres of cocktail sauce, the odour and flavour of the composition A are insipid.

By adding 3-dimethylaminopropylmercaptan the flavour is modified in an advantageous manner in that a note now emerges which is reminiscent of sardines and tuna fish (Composition B).

3-Dimethylaminopropyldisulphide can be used in the foregoing flavour in place of 3-dimethylaminopropylmercaptan.

Example 5 A brown meat sauce can be prepared as follows: 20 g of a mixture consisting of Parts by weight Dry meat extract, finely ground 18 Vegetable fat 15 Roast onion flavour 0.4 Salt 5.6 Sodium glutamate 16 Hydrolysed vegetable protein (e.g.

HPP, Type 3 H l, oil-coated or Type RF-B, oil-coated) 20 Caramel powder 1 Coriander powder 0.3 Marjoram flavour 0.1 Bay leaf flavour 0.12 Citric acid 0.28 Modified potato starch 23.20 100.00 are stirred in 1 litre of cold water and boiled while stirring continuously. After boiling for 3 minutes, the odour and flavour of this sauce are weak and uncharacteristic.

After adding 3-5 ppm of S-acetyl-3-dimethylaminopropylmercaptan, an excellent roast meat note is observed.

Example 6 A potato flavour composition can have the composition A or B: A B Parts by weight Valerianic 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 sulphide 20.0 Ethyl alcohol 928.0 928.0 1000.0 1000.0 A comparison of A and B shows that composition A is greatly inferior.

By partly replacing methional by (3-dimethylaminopropyl)-methyl sulphide an improvement in flavour emerges. Composition B has a pronounced potato note which is reminiscent of potato chips.

Example 7 A cheese aroma can have a composition A or B: A B Parts by weight Lactic acid 10 10 Ethyl butyrate 30 30 Ammonium isovalerate 30 30 i-Valerianic acid 50 50 Caproic acid 60 60 Butyric acid 120 120 (2-Dimethylaminoethyl)-methyl sulphide 5 Propyleneglycol 700 695 1000 1000 A comparison of A and B shows that the customary composition A is greatly inferior.

By adding (2-dimethylaminoethyl)-methyl sulphide, the cheese flavour in composition B is strengthened in an advantageous manner, the composition being 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 Nutmeg flavour 0.05 Clove flavour 0.05 Pepper flavour 0.05 Hydrolysed vegetable protein (e.g. HVP, Type 3 Hl and HVP, Type RF-B) 11.5 Vegetable fat (melting point 40"C) 17.0 Onion powder 1.0 100.0 is placed in 1 litre of hot water.

The flavour of this soup is weak and uncharacteristic. By adding 3-5 ppm of 2-diethylaminoethylmercaptan the meat flavour present is strengthened in an advantageous manner and, in addition, a pleasant roast meat note now emerges which harmonises well with the meat flavour.

Example 9 Imitation dry bacon pieces containing the following ingredients can be prepared: Parts by weight Coloured texturised soya protein (Miratex 405) 750 g Palm kernal fat (melting point 32"-34"C) 160 g Cooking salt 50 g Sodium glutamate 10 g Vegetable protein hydrolysate 25 g Pepper flavour 2.7 g Onion flavour 0.2 g Garlic flavour 0.1 g Smoke flavour 2 g 1000 g The ingredients, with the exception of the soya protein, are mixed well in a mixer with the molten palm kernal fat and dried, together with the soya protein, in a tumble drier at 35ops The granular mass solidifies upon cooling. This product can be used as an adjunct to, or replacement for, bacon in omelettes, with beans, in soups and sauces, in sandwiches and salads etc.

The product shows, however, a somewhat insipid and unspecific flavour. By adding 2-5 ppm of 2-diethylaminoethylmercaptan and/or 2-5 ppm of 2-diisopropylaminoethylmercaptan to the fat suspension, the imitation dry bacon pieces prepared therefrom have a meaty, smoky bacon-like pleasant character.

Example 10 An all-purpose seasoning powder containing the following ingredients can be prepared: Parts by weight Cooking salt 354 g Sodium glutamate 200 g Vegetable protein hydrolysate 200 g Maize starch 100, g Palm kernel fat (melting point 32"-34"C) 50 g Onion powder 50 g Yeast autolysate 25 g Turmeric powder 13 g 2-Dimethylaminopropylmercaptan (1% in propyleneglycol) 8 g 1000 g The turmeric powder is emulsified in the palm kernel fat and then blended with the remaining ingredients. The resulting powder is suitable for the seasoning of foodstuffs not only during cooking but also at the table.

By omitting the 2-dimethylaminopropylmercaptan there is obtained an uncharacteristic seasoning powder which lacks the desired meaty note.

Example 11 An extended cheese powder containing the following ingredients can be prepared: Parts by weight Cheese powder 500 g Pre-cooked maize starch 50 g Buttermilk powder 150 g Maltodextrin 285 g Cooking salt 4.9 g Citric acid 5g Sodium citrate 5 g (2-Dimethylaminopropyl)-methyl- sulphide (1No in propyleneglycol) 0.1 g 1000 g The ingredients are mixed, well to give a cheese-like product which is suitable for the seasoning of spaghetti, pizzas, soups, pastries, dip sauces etc.

When the (2-dimethylaminopropyl)-methylsulphide is not added, the product has a bland and insipid flavour.

Example 12 A ready seasoned hamburger helper mix containing soya protein can be prepared as follows: Parts by weight Textured soya protein (textured soya) (Miratex 210) 700 g and Palm kernel fat (melting point 32"-34"C) 70 g are mixed in a mixer-drier at 35"C and treated with: Cooking salt 30 g Sodium glutamate 10 g Vegetable protein hydrolysate 16 g Pepper flavour 2.3 g Onion flavour 0.5 g Garlic flavour 0.2 g 3-Dimethylaminopropyldisulphide (1No in propyleneglycol) 1 g.

By admixture of Egg powder 70 g and Dried onion flakes 100 g there is obtained of a stable powder which is mixed with 1090 g Minced beef 2400 g and Water 1600 g and fried in portions to give hamburgers with a pleasant rost meat odour.

If the 3-dimethylaminopropyldisulphide is not added, then the hamburger tastes weak and insipid. On the other hand, if the 3-dimethylaminopropyldisulphide is replaced by a similar amount of S-acetyl-3-dimethylaminopropylmercaptan, then an excellent roast meat note is realised.

The compounds of formula I (certain of which are novel and are the subject of Divisional Application No. 80 09252) (Serial No. 1590148) can be prepared in a manner known per se.

A summary of the preparative methods is given in the following Table: TABLE Temperature Method (*) Products (Formula I) Educts Solvent (e.g.) range (e.g.) B N,N-Dialkylamino- S-Acyl-dialkyl- (Educt brought Methanol, ethanol, 0 -100 C, -alkyl-mercaptan amino-alkyl- into contact propanol, water especially mercaptan (2) with the 20-65 C solvent, e.g. for a few minutes to several days) C N,N-Dialkylamino- Dialkylamino- Alkylmercaptan Base/organic 0 -100 C, -alkyl sulphide -alkyl halide solvent, especially especially (1) two-phase system 20-60 C NaOH/benzene, KOH/ benzene or NaOH ether, KOH/ether A S-Acyl-dialkylamino Dialkylamino- Thio-alkane- Organic, especially 0 -100 C, -alkylmercaptan -alkyl halide carboxylic aprotic solvent, especially (1) acid or salt e.g. chloroform, 20 -60 C (e.g. alkali water metal salt) E N,N-Dialkylamino Dialkylamino Oxidising NaOH/ether, as C -80 C to -alkyl-disulphide -alkylmercaptan agent, e.g. 100 C, I2, O2, H2O2 especially or organic or 10 -30 C inorganic peroxide D N,N-Dialkylamino Dialkylamino- Alkali metal NaOH/Benzene, as C 0 -100 C, -alkyl sulphide -alkyl halide hydrogen especially (1) sulphide 20 -60 C (*) See the following Examples.

(1) Chloride, bromide, iodine.

(2) Conveniently containing a readily cleavable acyl group such as formyl, acetyl, propionyl, benzoyl.

Example I (Method A) 100 g of 3-dimethylamino-1-propyl chloride hydrochloride are dissolved in 1.2 litres of chloroform and 192 g of triethylamine are added. 54 ml of thioacetic acid are added dropwise and the mixture is kept at the reflux temperature for 18 hours. The cooled solution is washed three times with 500 ml of 1-N sodium hydroxide and once with 500 ml of water. The aqueous phases are extracted with chloroform and the combined chloroform phases are dried, concentrated and distilled at 860-890C/10 mmHg. In this manner, 91.3 g (89.5%) of pure S-acetyl-3-dimethylaminopropylmercaptan are obtained.

The following compounds are obtained from suitable starting materials according to the same method: S-acetyl-2-diisopropyl aminoethylmercaptan: 102 -108 C/10 mmHg; and S-acetyl-2-dimethylamino propylmercaptan: 84"-87"C/11 mmHg.

Example 2 (Method B) 86.4 g of S-acetyl-3-dimethylaminopropylmercaptan are held at the reflux temperature for 15 hours in 900 ml of methanol. The methanol is then distilled off and the residue distilled at 1500-1550C under normal pressure. In this manner, 44.2 g (69% yield) of pure 3-dimethylaminopropylmercaptan are obtained; boiling point 42"C/10 mmHg.

The following compounds are obtained according to the same method: 2-Diisopropylaminoethylmercaptan: 720740/10 mmHg; 2-dimethylaminopropylmercaptan: 125"-145"C; 2-dimethylaminoethylmercaptan: 124"-128"C; and 2-diethylaminoethylmercaptan: 1600C.

Example 3 (Method C) 10 g of 1-dimethylaminopropyl-2-chloride hydrochloride, 100 ml of 2-N aqueous sodium hydroxide solution, 100 ml of benzene and 0.8 g of benzyl-triethylammonium chloride are introduced into a flask and ca 20 g of methylmercaptan are introduced for 40 minutes at room temperature while stirring. The mixture is then held at the reflux temperature for 4 hours. The benzene phase is concentrated and distilled, and gives, at 1650-1680C, 2.4 g (29% yield) of a mixture of [1-dimethylaminopropyl(2)J-methyl sulphide and 2dimethylaminopropylmethyl sulphide in the ratio of 15 to 85. The two products can be separated by preparative gas chromatography or column chromatography.

The following compounds are obtained according to the same method: 3-Dimethylaminopropylmethyl sulphide: 90 -100 C/25 mmHg; and 2-dimethylaminomethyl sulphide: 1300-1330C.

Example 4 (Method D) 10 g of 3-dimethylaminopropyl chloride hydrochloride, 100 ml of 2-N sodium hydroxide solution, 100 ml of benzene, 0.5 g of benzyl-triethylammonium chloride hydrochloride and 6.7 g of NaHS.H2O (70%) are held at the reflux temperature in a flask for 24 hours. The aqueous phase is then extracted three times with 50 ml of ether each time, the combined organic phases are washed with water, concentrated and fractionally distilled at 75"-85"C/0.025 mmHg. 1.35 g (21%) of 3-dimethylaminopropyl sulphide (are obtained in the form of a clear colourless liquid.

Example 5 (Method E) Iodine is added portionwise to a mixture of 4 g of 3-dimethylaminopropylmercaptan in 60 ml of ether and 30 ml of 2-N sodium hydroxide solution until the solution is no longer decolorised each time (ca 4.2 of iodine). After stirring for 1 hour, the ether phase is dried over magnesium sulphate, concentrated and fractionally distilled at 950-100OC/0.025 .mmHg.

2.7 g (68%) of 3-dimethylaminopropyl disulphide are obtained in the form of a clear colourless liquid.

The following compound is obtained according to the same method: 2-Dimethylaminoethyl disulphide: 1300-1320C/10 mmHg.

Claims

WHAT WE CLAIM IS:

1. A flavouring composition which contains as an essential flavour-imparting ingredient a compound of the general formula

wherein R1 and R2 each represent a C1~3-alkyl group, A represents an alkylene group which may be branched and R represents a hydrogen atom or the methyl, ethyl, formyl, acetyl or propionyl group or a group of the formula

in which A, R1 and R2 have the significance given earlier in this claim, in virtually pure form or in the form of mixtures (with the exception of mixtures which contain compounds of formula I and which originate from natural sources), together with at least one other flavour-imparting ingredient and/or a carrier or diluent.

2. A composition according to claim 1 which contains a synthetically prepared compound of formula I.

3. A composition according to claim 1 or claim 2, wherein R1 and R2 each represent the methyl group, A represents the ethylene or propylene group and R represents a hydrogen atom or the methyl group.

4. A composition according to claim 1, claim 2 or claim 3, wherein the compound of formula I is 3-dimethylaminopropylmercaptan.

5. A process for the manufacture of the flavouring compositions claimed in claim lj which process comprises adding a compound of formula I in virtually pure form or in the form of mixtures (with the exception of mixtures which contain compounds of formula I and which originate from natural sources) to known flavouring compositions or mixing a compound of formula I in virtually pure form or in the form of mixtures (with the exception of mixtures which contain compounds of formula I and which originate from natural sources) with natural or synthetic compounds or mixtures thereof suitable as constituents of flavouring compositions.

6. A process according to claim 5, wherein a synthetically prepared compound of formula I is used.

7. A process according to claim 5 or claim 6, wherein R1 and R2 each represent the methyl group, A represents the ethylene or propylene group and R represents a hydrogen atom or the methyl group.

8. A process according to claim 5, claim 6 or claim 7, wherein 3dimethylaminopropylmercaptan is used.

9. A method of imparting a flavour to materials, which method comprises applying to said materials or incorporating therein a flavour-imparting amount of a compound of formula I given in claim 1 in virtually pure form or in the form of mixtures (with the exception of mixtures which contain compounds of formula I and which originate from natural sources) or of a flavouring composition containing same.

10. A method according to claim 9, wherein a synthetically prepared compound of formula I or a flavouring composition containing same is used.

11. A method according to claim 9 or claim 10, wherein a compound of formula I in which R1 and R2 each represent the methyl group, A represents the ethylene or propylene group and R represents a hydrogen atom or the methyl group or a flavouring composition containing same is used.

12. A method according to claim 9, claim 10 or claim 11, wherein 3dimethylaminopropylmercaptan or a flavouring composition containing same is used.