Procedure for the Inlösungbringen of Phosphatiden in food oil

PATENT OFFICE PATENT SPECIFICATION No. 256597 class: 53 A 5/01 in. CI.: A 23 D Aus8abetag: 25. August 1967 A. NATTERMANN & CIE. IN K " LN (EUTSCHLAND) procedure for the Inlösungbringen announced of Phosphatiden in food oil on 12 December 1963 (A 9975/63); Priority of the registration in Germany from 29 December 1962 (N 22,555 IVa/53h) beampmeht. Beginning of the patent duration: 15.Feber 1966. During the production of food oils from the natural to oil the Phosphatide occurring always together with the oils is lost practically vöUig. This is for the memehliehe nutrition a sehwerwiegender loss, because the Phosphatide as well known is from crucial biological effectiveness. It was not missing therefore at efforts to win from vegetable oils so-called VolIöle yields the valuable natfirliehen escort substances, as Phosphatide contain, practically invariably. The analysis of a handelslibliehen coldly pressed Sonnenblumenöles resulted in meanwhile only a Phosphafidgehalt of 0, 06%, a quantity, which is much too small, in order to have been able a physiological effect. Ss was surprisingly found that arbitrary quantities of Phosphatiden can be brought in food oil by means of natural occurring Feuderivate in Lömng, if one uses Monoglyeeride or such containing Glyeeridgemisehe as fat derivatives, whereby the Monoglyeeride exhibits at least 50%, preferably more than 80% insatiated fatty acids. Since the Lösungrvermögen of these Monoglyeeride is not impaired fär Phosphatide in SpelseO1 thereby as it was found that one uses the Monoglyeeriä in the mixture with Diglyeeriden and/or Triglyeeriden, can be used lfi also in the trade the available, Monoglyeeride of products specified, the nearly always C-emisehe of mono, Dlund Triglyeeriden is. Commercial Monoglyeeride contained depending upon its production single-borrowed 45 - 60% Monoglyeerid. The content of Monoglyeerid up to over 90% can be increased by molecular distillation. For the Zweek of the invention to win phosphatidhaltäge food oils it is of great importance that this Glyeeride, particularly Monound Diglyeeride, is natürlieherweise occurring, also fat connections constantly existing in the human organism. It to find do not see only therefore no more in the practice-borrowed food oils, because Monound Diglyeeride is lost with the refining of the fats and/or oils. Brit. Patentsehrift No. 260, 108 concerns a procedure, by means of which Verändemngen arising relatively easily in hoehgereinigten vegetable oils (Ranzidität and ranziger Gesehrnaek) zutttekgehalten and which are improved Lagereigemehaften of such oils. In addition directly smallest quantities of “Leeithin” are to be inserted into the oil freshly cleaned according to the usual refining methods. In this connection it is to be still noticed that the traces 0, 05 - only to approximately 1/5 work-borrowed 0, 1% kind Leeithin, which was recommended to admit in this procedure oils, consisted of Leeithin = Cholinphosphatid. It remains unclear whether at all a real clear and/or remaining clear solution could be obtained. The German Patentsehrift No. 516,119 concerns a procedure for the processing of Phosphatiden in margarine. It concerns to solve Phosphatide in oxidized and/or polymerized oils and to then add this solution the margarine. To the Irdösungbringen an additive from 25 to 50% is more oxidize or more polymerized oils necessarily. This procedure is more than precarious lebensmirrelreehtlieh, because the spontaneous occurrence of oxidized and polymerized oils, which require-borrowed here in so high concentrations as a solution mediator is, is valid to prevent it straight in 8peiseölen, there such verän - 2 - NR, 256597 derten Umbaubzw. Dismantling products of oils with insatiated fatty acids from the physiological point of view as well known are unwanted. Succeeds according to invention with the help of completely besümmter Monoglyceride. thus substances, which occur in the normalphysiologisohen happening to solve arbitrary rougher quantities of Phosphaüden in food oils clearly and stably. If a high concentration of Phosphatid is erväinscht in the Slmiseöl, it is appropriate to use as pure a Monoglycerid as possible or a Glyceridgemisch with as high a content of Monoglycerid as possible as solution mediators because a too large content in the oil at e.g. a Partialglyceridgemisch consisting of Monound Diglyceridgemisch because of the Diglycerids disadvantageously the taste of the oil affect and also to a fine precipitation can lead. One can solve the Phosphatide also by Monoglyceriden, which exhibit predominantly satisfied fatty acids, under warming up in oils. These solutions are not meanwhile stable, because this Monoglyceride fails with the cooling of the solution partly again. It was found that from the commercial mixtures from mono, Diund Trlglyceriden like lfi in addition, at the Partialglyceriden the Monoglyceride with a content of ungesärtigten fatty acids, particularly suitable for the purposes of the invention, of at least fi0, preferably however from more as 80%, in a simple manner by a dialysis of such a mixture by a rubber below against petroleum ethers than solvents to be won being able, since in this way an enrichment from Monoglyceriden to i00*] is possible for 0. For this purpose the Glyceridgemisch is eingeflillt in the melted condition or solved in few Pel more oläther, into a dütmwandigen Gummisehlauch, these and are not subjected in a Soxhletapparat of dialysis against petroleum ethers are afterwards not tied. Hiebei pass Triund Diglyceridmoleküle the rubber below substantially more rapidly than the Monoglyceride. In the Dialysat rich thus Triund Diglyceride on, selecting in the rubber hose depending upon duration of dialysis for instance a 90oder even 100 of oiges Monoglycerid stays itself. The separation is not quantitative, since also something Monoglycerid goes through the diaphragm. For the improvement of the yield the first Dialysat can be geftilit after the evaporation of the largest part of petroleum ether again into the rubber hose and subjected to a second dialysis. As examples of Phesphatiden which are applicable for the purposes of the invention are mentioned: Commercial Phosphatide, which are called despite its Kephalingehaltes Lecithin; in the procedure of the German patent specification Nr.1 047597 1957 kephalinarmen natural Cholinphosphorsäurediglyceridester won from 10. July; and in the procedure of the German laying out writing 1,058,299 received kephalinfreien natural Cholinphosphorsäurediglyceridester. This kephalinarmen and kephalinfreien natural Cholinphosphorsäurediglyceridester is characterised by one besortders high content of the vital essential fatty acids, which increases its ernährungsphydologische effect compared with commercial Phosphatidgemi substantially. The production of the kephalinarmen natural Cholinphosphorsäurediglyeeridester from vegetable Rohphosphatiden, in particular Sojabohnenrohphosphadden, takes place in the procedure of the German patent specification No. 1,047,597 via extraction with Aceten and afterwards with alcohol with a 85oc not exceeding temperature and under exclusion from air and/or oxygen in presence of an inert gas in the way that in the vacuum and in presence of an inert gas of acetone released extraction arrears of a repeated extraction with alcohol subjected, which alcoholic solutions several days left untouched, then from the suspended and/or colloidal along-solved materials is released and finally restricted in the vacuum when simultaneous pulling an inert gas tight. In addition, these alcoholic solutions can be given in the procedure of the German Anslegeschrift 1 0SB to 299 4fi for separation of the Cholinphosphorsäurediglyceridesters from the Kephalin under exclusion from light, air and/or oxygen over a column, which is filled with an alcoholic bloating of an oxide and/or a carbonate one or several elements of the IITH and IIITH group of the periodic system, is eluiert then the bloating with alcohol and finally restricted the alcoholic solutions running off in the vacuum in presence of an inert gas. As food oils refined oils or fats, as in addition, the so-called nature-left fats or oils, are applicable furthermore germ oils or other Rohund of full oils suitable for the nutrition for the purposes of the invention. Advantage procedures invention lies therein that relatively very small quantities of Monoglyceriden, which exhibit a content of at least 60%, preferably however from 80 /o of insatiated fatty acids ausreiehen, in order to receive completely clear and stable solutions from Phosphatiden in a Konzentratien, which is physiologically effective. Can do e.g. in 100 Gew. - Parts of a Genuf 51s by means of a Gew. - Part of Monoglyeerid 2 thread - parts of a kephalinarmen natural Cholinphosphorsäurediglyceridesters or 3 thread - parts of a kephalinfreien natural Cholinphosphorsäurediglyceridesters in solution to be brought. If one turns the double quantity of Monoglycerid on, also the double quantity of Phosphatid can be solved. The release effected favourable-proves under protection from light and air on use of an inert gas under gentle Erwarmen and agitating. Furthermore it is appropriate to add to the mixture vitamin E as Antloxydans. Since already 500 mg after the German patent specification of a Nr.1 are effective 047,597 received kephalinarmen natural Cholinphosphorsäurediglyeeridesters, one needs one daily amount of 25 g to supply to the human body from an oil, which contains 2% those lake of concentrate, only. Such a quantity lies in the context of usual daily consumption. B e i s p i e 1 1st 50 g of a commercial Monoglycerides with a Monoglyeeridgehalt from approximately 55 to 60%, which in all other respects consists of Dlund Triglyceriden, are solved in few Peuoläther and given into a thin-walled rubber hose. This is carefully locked with a thin cord and dialysiert in a Soxhletapparat about 24 h against petroleum ether (3060oc). After opening the dialysis arrears are released by Destillatien, last in the vacuum, from petroleum ether. 23 g with a Gehah at Monoglyceriden from 87 to 88%o remain. If one dialysiert about 48 h against petroleum ethers, remain 10 g dialysis arrears, which consist of pure Monoglycerid. In order to increase the yield, the Dialysat received after 48 h can be dialysiert against petroleum ethers. One goes to z. I3. of 100 g of the Dialysates released from petroleum ether out, then this is dialysiert in a Gummischlaueh 70 h against petroleum ethers. One receives 23 g dialysis arrears with a content from 90% at Monoglyeerid. For the determination of the Monoglyceridgehaltes 500 mg of the dialysis arrears are separated by chromatography at a Florisil column according to K.K. CARROLL (J. Lipid Research 2, I85). B e i s p i e 1 2: 100 g Glyceridgemi indicated in example 1 are brought by gelindee warming up on the Wasserbad to melting; into a rubber hose filled and this locked and into the Soxhlet about 50 h against petroleum ethers dialysiert. The Dialysenrüekstand amounted to 35 g with a content of Mortoglycerid of 91, 6%. For the increase of the yield the Dialysat, like with the example 1, can be indicated be dialysiert in the rubber hose against petroleum ethers. B e i s p i e 1 3: 1 kg of Sojaöl is shifted with 10 g one for instance 91%o Monoglycerid, which exhibits 87qo insatiated fatty acids, containing Glyceridgemisehes and then to 15 g only of the oil released Sojabohnenphosphatid under agitating and if necessary under warming up on a Wasserbad from 40 to 500 C under protection by an inert gas, favourable-proves also under exclusion of light, in solution brought. B e i s p i e 1 4: , As indicated in the example 3, a solution of 18 g of a out vegetable Rohphosphatiden is manufactured Monoglyeerid, which exhibits 92°/o insatiated fatty acids in the way manufactured kephalinarmen nafärliehen Cholinphosphorsäurediglyceridesters indicated above in 1 kg corn germ oil using 10 g of a Glyeeridgemisehes as a content by for instance 91°7. Example 5: In the way indicated in the example 3 a solution of 50 g is manufactured above one like indicated nascent kephalinfrelen natural Cholinphosphorsäurediglyceridesters in 2 kg Sonnenblumenöl using 20 g Glyceridgemi as a content by approximately 91% Monoglyeerid, which exhibits 92% insatiated fatty acids. B e i s p i e 1 6-- Under agitating and easy warming up 90 g of a kephalinarmen natural Cholinphosphorsäurediglyeeridesters and 200 g of a Glyceridgernisehes with a content from approximately 55 to 60% Monoglycerid, which 53% ungesttttigte fatty acids exhibits, are mixed and this mixture in 5 kg preheated Erdnul3öl is given and agitating and received also in this case a clear and stable solution is continued. The invention concerns also the procedures won solutions of Phosphatiden in food oils, managing described after that.