DE1030329B - Process for the production of the lactone of O € -oxydodecanoic acid (ª € -oxylauric acid) serving as a flavoring agent - Google Patents

Description

GERMAN

The invention relates to a process for the preparation of the straight-chain <5-oxydodecanoic acid lactone, which is suitable for use for the flavoring of fatty or fatty foods. The starting point here is an-heptylcyclopentanone ¹ , which can be converted directly into the lactone using peroxymonosulphuric acid ("Caro's acid") or a mixture of concentrated sulfuric acid and hydrogen peroxide. The an-heptylcyclopentanone can also be oxidized to (3-keto-n-dodecanoic acid, preferably by means of chromic acid. The keto acid obtained in this way is converted into o-oxy-n-dodecanoic acid by reduction, from which the lactone is then obtained by splitting off water .

The lactone obtained according to the process according to the invention is used, for example, in margarine to impart a butter-like taste and smell, with the possible formation of the lactone from the <5-oxy-n-dodecanoic acid or its salts in the margarine itself with the participation of the components the margarine can be made. This process takes place, for example, when heating a fat that contains the oxy acid or its salt and free acid, e.g. B. at temperatures of 100 to 200 ° C instead.

The substances previously used for flavoring, such as. B. diacetyl or butyric acid are against oxygen sensitive and / or very volatile. In contrast, this is noticeable according to the method according to the invention obtainable lactone is characterized by the fact that it is practically not sensitive to oxygen and less easily volatilized.

By adding the lactone of <5-oxydodecanoic acid can be an extraordinarily sweet and well-rounded flavoring of fats or fatty foods Food. A particular advantage of using the above Lactons consists in that, although the flavor developed in the fat as such is not pronounced is strong, when the fat is heated, the typical roast smell and taste of butter is preserved. With the addition of the lactone, you are for the first time able to smell that typical buttery smell or smell. -to achieve taste. The proportions of lactone that are required to produce this special aroma To obtain heating is approximately 5 to 20 parts by weight for every 1 million parts by weight of the fat. At these proportions the direct aroma, i.e. H. the aroma of the fat as such, d. H. without heating, also improved, but not to a marked extent. The property of the mentioned lactone, To produce the aforementioned roast smell and taste when heated when added to the fat is very good permanent nature, and accordingly, has d'ie ver procedures for the production of the lactone of <5-oxydodecanoic acid (<5-oxylauric acid) which is used as a flavoring agent

Applicant: Unilever N.V., Rotterdam (Netherlands)

Representative: Dr. E. Wiegand, Munich 9,

and Dipl.-Ing. W. Niemann, Hamburg I ₁ Ballindamm 26,

Patent attorneys

Claimed Priority: UK 8 Aug 1 & 52

Reginald James Taylor, Heswall, Wirral, Chester, William T. Weller, Eastham, Wirral, Chester

(Great Britain),

Jan Boldingh, Pauline Haverkamp Begemann, Dordrecht, and Guido Lardelli, Rotterdam (Netherlands),

have been named as inventors

application of the lactone of (5-oxydodecanoic acid special Advantages for baked goods or for fats that are to be used for cooking or frying purposes.

Compared to previously known Aromatisierungsgemischen such as diacetyl with butyric acid, also includes the obtainable according to the invention lactone on the advantage that comes with it 'products flavored at a higher _pH value can be adjusted, which z. B. is of particular value in terms of avoiding undesirable taste nuances in the presence of nitrogen-containing compounds.

Serving as starting material a-n-heptylcyclopentanone can, for. B. by implementing Cyclopentanone with n-heptanal to oxy-n-heptylcyclopentanone, its dehydrogenation to a-n-heptylidenecyclopentanone and its hydrogenation to a-n-heptylcyclopentanone getting produced.

Another production method leads to dialkyl adipates via carbalkoxycyclopentanone to n-heptylcarbalkoxycyclopentanone, which then becomes the corresponding acid is saponified, which is then decarboxylated to give heptylcyclopentanone.

A third production method leads from the lactone of γ-oxy-n-dodecanoic acid to a mixture

8091527 / Ψ74

pentanone sourced, received and had the same physical Properties like the product obtained according to Example 1.

Example 3

n-Heptyleyclopentanonen, which by hydrogenation also be converted into the heptylcyclopentanone. The method of the present invention is as follows explained in more detail using a few examples in which parts mean parts by weight. .

50 g of cr-heptylcyclopentanone were added to an ice-cooled mixture of 200 g of sulfuric acid and 200 g ethyl alcohol are added and 70 g 30% hydrogen per-

Gisdhem stirring at 30 ° C using "Caro's acid", io oxide added drop by drop. Subsequently was which consists of 4.4 kg of potassium persulfate, 20 kg of 77% for 3 hours, the temperature between 0 and 15 ° C was maintained. After standing for 1 hour at 15 ° C., the mixture was diluted with 1.5 l of water and then stripped with petroleum ether. Extracted after distilling petrol and distilling off the extractant- 15 Heren of the petroleum ether, the residue consisted of " lates. The residue, which polymeric by-products, unconverted starting material, <5-oxyducts contained, was used to reconvert such ethyl decanoate and lactone. This residue By-products in the monomer with alkali (52 g) was saponified with alcoholic potassium hydroxide and saponified, then acidified and the neutral components extracted with ether using gasoline. Nacft extracted. The extractant was distilled off, the acidification was extracted again with ether " the residue is first heated to 100 ° C / 20 mm, the ether is distilled off from the extract and the

Residue heated to 100 ° C / 30mm. By fractionation the residue in vacuo was the lactone of (5-oxydodecanoic acid in a yield of received about 50%; it had the same physical properties as that of Example 1

example 1

- 2 kg of an-heptylcyclopentanone were under ener-

Sulfuric acid and water was produced, oxidized. After completion of the reaction, 101 Water added. The solution thus obtained was with

and finally the lactone of (5-oxy-n-dodecanoic acid distilled over at 124 ° C under a pressure of 0.8 mm Hg. The lactone yield was 75% on a basis on the a-n-heptylcyclopentanone used. The lactone had the refractive index w | ° = 1.4596.

hold product.

Example 4

30 g (5-n-heptylcyclopentanone were mixed with 20 g Potassium permanganate, which was dissolved in 250 ecm acetone, for 3 hours at a temperature of Maintained 50 ° C. The manganese dioxide formed was filtered off and extracted with acetone. After that it was

Example 2

1 part of an-heptylcyclopentanone was mixed with 1.3 parts of chromic acid, which was dissolved in 11 parts of 35% sulfuric acid
acid was dissolved at a temperature of 30 ° C
oxidized within half an hour. It was
a yield of 60 to 70% calculated on the
Heptylcyclopentanone, an (5-keto-n-dodecanoic acid. This cS-keto acid was distilled off from the reaction, the solvent and a yield mixture extracted with xylene and the extraction of <5-keto-n-dodecanoic acid from 10 to 15 acid was then dissolved in light petroleum <5-keto acid was then dissolved in light petroleum (|% based on the medium partially distilled off in vacuo the <5-keto-to-heptylcyclopentanone calculated received "■ d i.. (b.p. 70 to 9O ⁰ C.) Cap. 70 to dissolved at a temperature of 70 ° C. After down- 90 ° C.) dissolved at a temperature of 70 ° C. After cooling this solution to room temperature, the (5-keto- n-dodecanoic acid, which was filtered off the (5-keto-dodecanoic acid, which was filtered off. Yield 60%. Yield 9%. The <5-keto-

The cS-ketododecanoic acid thus obtained was then n-dodecanoic acid was then in the same manner as, with the same amount by weight of aluminum isopro- in the example. 2 processed to lactone. The Off ¹ Pylat in ten times the amount of isopropyl alcohol at 45 yield was 8%, reduced to the used Heptyleiner at-temperature of 80 to 82 ° C, wherein cyclopentanone based. .%

a mixture of aluminum compounds of (5-oxydodecanoic acid and isopropyl <5-oxydodecanate received. The isopropanol was then distilled off and the acid-ester mixture obtained was also distilled off Treated 4 parts of a 25% strength aqueous sodium hydroxide solution. The isopropanol formed was distilled off again, with, based on 20 g (5-keto-n-dodecanoic acid calculated as the starting amount, 21 g of one Mixtures of the sodium salt of (5-oxydodecanoic acid and sodium aluminate were obtained.

Claims (1)

Claim. To this mixture was added 5% aqueous hydrochloric acid until it had a _pH value of Figure 1. The lactone-oxycarboxylic acid mixture was extracted with benzene and the extractant was distilled off. Lactone formation was completed by heating the residue to 100 ° C under a pressure of 20 mm Hg. The pressure was then reduced to 1 mm and the lactone of (5-oxy-n-dodecanoic acid was distilled off (boiling point ₁ = 126 ° C.). In a yield of 50%, the an-heptylcyclo- Process for the preparation of the o-oxydodecanoic acid lactone (cS-oxylauric acid lactone), which is used to flavor foods that contain fat or consist of fat, characterized in that an-heptylcyclopentajnone is either added directly by means of peroxymonosulphuric acid ("Caro's acid") or a mixture of concentrated sulfuric acid and hydrogen peroxydic acid to the lactone or, preferably by means of chromic acid, to (5-keto-n-dodecanoic acid, and this is converted by reduction into the (5-oxyn-dodecanoic acid, which is then lactonized in a manner known per se. - _f Considered publications: Beilstein, "Handbuch derorganischen Chemie", 4th edition, Vol. Ill, pp. 323, 334, 343. When the application was announced, 1 declaration of priority transfer was laid out. © m 527/474 p.