DE1205511B - Process for the separation of cane sugar mono- and diesters of saturated or unsaturated fatty acids with 6 to 30 carbon atoms - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

int. α .:

C07c

German class: 12 ο - 6

Number: 1205 511

File number: L 43303IV b / 12 ο

Filing date: October 27, 1962

Opening day: November 25, 1965

Various methods for the production of cane sugar esters are already known. You insist in a transesterification of lower alkyl esters of monobasic fatty acids or natural or synthetic glycerides with cane sugar. When reacting 1 mole of 5 of the selected ester or glyceride with 3 moles Cane sugar is primarily formed from the cane sugar monoester, while in the implementation of 3 mol Esters or glyceride with 1 mole of cane sugar are predominantly formed from cane sugar diesters. the Transesterification is generally carried out in the presence of small amounts of a basic catalyst, such as anhydrous potassium carbonate, in an anhydrous high-boiling solvent that is aromatic, aliphatic or can be heterocyclic and contain or contain at least one amide or one amino group Dialkyl sulfoxide, e.g. B. dimethylformamide.

The last traces of the solvent, the toxicity of which is the use of the end products in food would prevent, are removed according to the method of patent 1158,486 that the raw mixture is dissolved in a mixture of butanol and cyclohexane, which after filtration with water pulled out and evaporated to dryness.

The ester mixture is freed from unconverted or partially converted starting material, ie cane sugar, esters or partial fatty acid glycerides, using the method of patent application L 42934IV / 12 ο by dissolving it in a lower alkyl acetate at elevated temperatures and increasing the hot solution to about 30 to 9O ⁰ C heated water is extracted, wherein the unreacted cane sugar passes into the aqueous phase, which is removed hot. The organic phase is ^{cooled to 0 to 30 °} C. and extracted with water at this temperature, a pure mixture of cane sugar esters passing into the aqueous phase, from which it is obtained in a known manner.

Despite extensive investigations in which the reaction times, the molar ratios of the reactants, the temperatures, yields, etc. were precisely determined, few attempts have been made to achieve the individual products in an essentially pure state. If the processes described in the literature for the production of cane sugar esters were repeated in detail, it was previously never possible to produce cane sugar monoesters or diesters in the pure state. Indeed, regardless of whether monoester or diester was tested, the analysis always showed mixtures of these products. The mono- esters produced by known processes gave cloudy solutions, which indicates the presence of a high percentage of diesters, since processes for separating cane sugar mono-
and diesters more saturated or unsaturated
Fatty acids with 6 to 30 carbon atoms

Applicant:

Ledoga S. p. A., Milan (Italy)

Representative:

Dr. W. Beil, A. Hoeppener and Dr. H. J. Wolff,

Lawyers,

Frankfurt / M.-Höchst, Adelonstr. 58

Named as inventor:

Luciano Nobile, Tullio La Noce, Milan (Italy)

Claimed priority:

Italy of October 31, 1961 (19 682)

these do not dissolve in water, but rather result in dispersions with a slimy or cloudy appearance. As a result, a process was necessary by which the cane sugar monoesters and diesters of let each other separate.

The invention relates to a method for the separation of Rohrzuckermono- and diesters of saturated or unsaturated fatty acids having 6 to 30 carbon atoms which ester is dissolved a portion of the mixture in about 3 parts of ethyl alcohol at a temperature of about 40 ⁰ C to about Rückfiußtemperatur, on The solution obtained in this way cools to temperatures between 0 and 35 ° C, separates the precipitating cane sugar diesters of the saturated acids with at least 16 carbon atoms, evaporates the alcoholic solution, dissolves the residue in about three times its weight in ethyl acetate, the solution obtained in this way Cools to about 5 to 20 ° C, separates the precipitated cane sugar monoesters, evaporates the solution to dryness and the cane sugar diesters of saturated fatty acids with a maximum of 14 carbon atoms and the diesters of cane sugar with unsaturated fatty acids are obtained as residue.

The inventive method can both with the by transesterification of cane sugar with the reaction mixtures obtained with lower alkyl esters of fatty acids as well as with the more complicated ones Reaction mixtures are carried out by

509 739/414

Transesterification of cane sugar with natural fats and is friable and easy to grind into powder. Fatty oils can be achieved. The cane sugar dipalmitate dispersed in water and

The starting material for the process of the result is slimy solutions. The alcoholic solution, Both mixtures, which predominantly contain the cane sugar monopaneity, are suitable for the finding Contain diesters, as well as those in which the proportion 5 evaporated to dryness. ^ The product is through is larger on monoesters. Recrystallize from ethyl acetate. 243 g

In the known processes for converting cane sugar monopaneity, cane sugar monoesters or diesters are predominantly obtained in the solid state in the form of a crumbly and easily pulverizable substance removed from cane sugar with a lower alkyl ester. The cane sugar mono, depending on whether the molar ratio of sugar to alkyl "palmitate" dissolves in water and results in only slightly thickest 3: 1 or 1: 2. The use of a liquid, clear, transparent solution.
Excess cane sugar favors the formation of _. · Ι ο

Mono-star, d. H. of products that can easily be divided into B e 1 s ρ 1 e 1 2

Dissolve water and give clear solutions. If you 500 g of a mixture of cane sugar mono- and

Cane sugar with a natural triglyceride in 15 -diestearate, which after a similar to that in approximately molecular amounts, z. B. 1 mole of tri Example 1 for the production of cane sugar palmitate glyceride and 1.5 mols of cane sugar, can react, the method described was prepared, is mainly obtained in diesters. In contrast to this, 1500 ecm of 95% ethyl alcohol with stirring and are formed when 1 mol of triglyceride is reacted with heating in a reflux condenser. The plurality of moles obtained cane sugar, for example, 1 mole of triglyceride 2 ° off solution is gradually, with stirring, at 30 ⁰ C and 6.5 moles of cane sugar, sugar cane mainly cooled. The precipitate is filtered monoester under vacuum. and washed with ethyl alcohol. That way

Distearate (300 g) obtained by the process of the present invention is further purified by recrystallization, mixtures of 95% ethyl alcohol prepared in a known manner. By monoesters and diesters in ethyl alcohol, e.g. B. 25 dispersing the product in water gives 95% ethyl alcohol at a temperature of slimy solutions. The alcoholic solution which dissolves 50 to 90 ° C. The cane sugar monostearate obtained in this way becomes dry. Solutions are gradually evaporated to temperatures of. The cane sugar monostearate (200 g) cooled to 35 to 0 ° C. If a sugar ester is one in the solid form, it is purified by recrystallization from fatty acid having 18 carbon atoms or more pre- 30 ethyl acetate. The monostearate is a white, is preferably cooled to 20 to 30 ° C, crumbly and easily pulverizable material, which dissolves more completely while esters of fatty acids with lower dissolves in warm water and transparent Lö number of carbon atoms results,
separation by stronger cooling (up to about O ⁰ C) Example 3

achieved. In this way it is possible to create extraordinary 35

lent to produce pure monoesters and diesters, so that 500 g of the product from the transesterification of 1 mol

z. B. the monoester a perfectly clear and thorough ox tallow, (the acid content of which was as follows: visible solution in water results. Myristic acid 3%> myristolic acid 1 ⁰ _{I 0} , palmitic acid

According to the process of the invention, 1 part of the 26%> palmitoleic acid 6%, stearic acid 17%> oil sugar ester is added by heating in 3 parts of ethyl alcohol, 40 acid 43% ^and linoleic acid 4%) with 1.4 mol of raw material. B. 95% ig ^e m ethyl alcohol dissolved, and the solution is sugar, the process of dimethylformamide and cooled ^{to 35 to 0 0} C according to the process described in patent 1158 486 depending on the nature of the original fatty acid residues. As a result, the diesters are precipitated by the process described in patent application L 42934IV b / 12 ο of the saturated fatty acids with 16 carbon atoms from the not or only partially or more that may have been formed, 45 wise converted glycerides are purified during with diesters of unsaturated fatty acids by refluxing in 1,500 cc dissolved 95 ° / _o sodium or with saturated fatty acids, the chains of less ethyl alcohol. The resulting solution will have 16 carbon atoms when mixed un- cooled with water and ice to 5 ° C. Which remain in solution on a pure monoester. This solution filter precipitate collected under vacuum is evaporated to dryness, and the obtained solid so washed with chilled ethyl alcohol and weighs product is recrystallized from ethyl acetate, from which, after drying in a vacuum oven, 265 g. only the monoesters of both the saturated and the The product, which mainly consists of dipalmitate unsaturated fatty acids precipitate on cooling. and distearate is a white, crumbly and _. · 1 1 easily pulverizable material. It can be immersed in water

ispie 55 and gives slimy solutions. the

500 g of this mixture of cane sugar mono- and alcoholic solution is evaporated to dryness, dipalmitate, which is obtained after the product described in the above and 235 g of a dense yellow oily patent application L 42934IV / 12 o. This product is prepared by dissolving drive is 1500 cc 95 ° / _o dissolved in ethyl acetate and precipitation at -20 ⁰ C cleaned. Ethyl alcohol with stirring, at a temperature 60 The result is that hauptvon 40 achieved a dense oily product to 50 ⁰ C. The resulting solution is composed of dioleate, which is resistant - z. B. with water and ice - gradually results in an emulsions in water.
Temperature of 5 ⁰ C cooled and continuously. .

touched. The precipitate is removed under vacuum. B e 1 s ρ 1 e 1 4

filtered and twice with chilled ethyl alcohol 65 300 g of the product from the transesterification of 1 mol washed. The product is also by ox tallow (composition see Example 3) and 6.4 Crystallization from ethyl alcohol further purified, and moles of cane sugar, which is already made from dimethylformamide one receives 255 g of dipalmitate in solid form, which and not or only partially converted starting material

material was freed, are dissolved by heating in 900 ecm 95% ethyl alcohol. The solution is cooled to a temperature of 5 ^{° C. with water and ice.} The white precipitate is collected and dried. 75 g of a solid mixture are obtained, which mainly consists of cane sugar dipalmitate and distearate. The product is friable and easy to pulverize. It dissolves in water to form cloudy and slimy solutions. The filtrate (alcoholic solution) is evaporated to dryness and 225 g of a very hygroscopic yellow product are obtained. This product, which consists of a mixture of oil monoesters and diesters of cane sugar, is dissolved in 675 ecm of ethyl acetate by applying heat. The solution is cooled to 1O ⁰ C, and the precipitate is collected and dried. 180 g of a yellow product are obtained which mainly consists of a mixture of cane sugar monoesters of palmitic, stearic and oleic acid. The yellow product is dissolved in warm water and results in a clear and transparent viscous solution. The filtrate (ethyl acetate solution) is evaporated to dryness, and 45 g of an oily yellow viscous product are obtained, which mainly consists of cane sugar dioleate. The dioleate is purified by crystallization from ethyl alcohol at -20 ^0C. The dioleate gives permanent emulsions in water.

Example

350 g of the transesterification of 1 mole of palm oil (with approximately the following composition:. Myristic acid 1%, palmitic acid 48%> stearic acid 4 ° / ₀ oleic acid 38%, and linoleic acid 9%) and 6,4MoI cane sugar, the dimethylformamide and the not already of or only partially converted starting material was purified, were dissolved under reflux in 1400 ecm of 95% ethyl alcohol. The resulting solution is gradually cooled to 5 ° C. with ice and water. The precipitate is collected and dried. In this way 37 g of cane sugar dipalmitate are obtained, which after crystallization from ethyl alcohol is a crumbly white solid which can easily be ground to a powder. The alcoholic solution is evaporated to dryness, and 310 g of a solid mixture are obtained, which consists of cane sugar monoesters and diesters, mainly of oleic acid. 300 g of the mixture are dissolved in 900 ecm of ethyl acetate with the aid of heat. The resulting solution is cooled to 1O ⁰ C. The precipitate consists mainly of cane sugar monopalmitate and monoleate (200 g) and is filtered and dried. The yellow product is a crumbly solid that can easily be ground into a powder. These monoesters dissolve in warm water and give clear and transparent viscous solutions. The ethyl acetate solution is evaporated to dryness, and 100 g of a viscous yellow, oily product are obtained, which consists mainly of cane sugar dioleate and dilinoleate. These latter products are cleaned by dissolving it in 20 cc of ethyl acetate, which is then cooled to -2O ⁰ C. The precipitate (67 g) is filtered at -20 ⁰ C and dried under vacuum in an oven at 50 to 6O ⁰ C. In this way, the dioleate is obtained as a yellow semi-solid mass.

Claims (1)

Claim: A method for separating Rohrzuckermono- mono- and diesters of saturated or unsaturated fatty acids having 6 to 30 carbon atoms, characterized in that said ester is dissolved a portion of the mixture in about 3 parts of ethyl alcohol at a temperature of about 40 ⁰ C to about the reflux temperature, which in Solution obtained in this way cools to temperatures between 0 and about 35 ° C, separates the precipitating cane sugar diesters of the saturated acids with at least 16 carbon atoms, evaporates the alcoholic solution, dissolves the residue in about three times its weight in ethyl acetate, which was achieved in this way The solution cools to about 5 to 20 ^° C., the precipitating cane sugar monoesters are separated off, the solution is evaporated to dryness and the cane sugar diesters of saturated fatty acids with a maximum of 14 carbon atoms and the diesters of cane sugar with unsaturated fatty acids are obtained as residue. Considered publications:
U.S. Patent No. 2,893,990. Legacy Patents Considered:
German Patent No. 1158 486.