DE1518246C - Process for the production of sucrose esters of substituted stearic acids - Google Patents

Description

The. Invention relates to a process for and mixtures containing such acids or esters Production of sucrose esters of substituted can be produced from natural fats or Stearic acids with at least one hydroxyl group are known technical products. For example in the chain, which can also be mentioned by an epoxy or alkoxy: epoxidized oleic acid (9,10-epoxy group can be substituted. 5 stearic acid), epoxidized ricinoleic acid (12-hydroxy-

Processes for the production of sucrose-9,10-epoxystearic acid, epoxidized soy fatty acid, esters are known which start from saturated and unsaturated epoxidized linseed oil fatty acids, epoxidized tall oil fatty acids. In this process, sucrose acid, epoxidized castor fatty oleic acid and the deesterified lower-speaking methyl, ethyl, propyl or butyl esters by transesterification of fatty acid esters are used. Alcohols with cane sugar in the presence of a strong io If these epoxy fatty acids or their esters are catalytically hydrogenated with polar organic solvents and an alkali _ hydrogen at elevated pressure, metallic catalyst at temperatures of 120 to, for example, according to the in J. Org. Chem., Vol . 18 (1953) obtained 18O ⁰ C. These sucrose esters of saturated p. 686 to 692, described processes, so arises on or unsaturated fatty acids are suitable as a non-place of the epoxy group a hydroxyl group,
ionic detergents and emulsifiers. You have 15 in the hydrolysis of the epoxy fatty acids or their against the commercially available synthetic esters with water in an alkaline solution, for example table detergents, in particular on the basis of according to the in J. Am. Chem. Soc, 70, pp. 1235 to 1240 dodecylbenzenesulfate, because they (1968), described methods, the epoxy will be inferior in their properties to the epoxy. group to vic. Glycol. Monoepoxy fatty acids, or their

Surprisingly, this does not apply to sucrose esters, resulting in the corresponding dihydroxy fatty acid esters of substituted stearic acids with at least or their esters. Similar to the rings of a hydroxyl group in the chain. While the mouth with water passes the annular gap having ζ Saccharoseester of saturated and unsaturated lower alcohols such as methyl, ethyl or propyl '- fatty acids, the surface tension of the ^ water of alcohol, leading to the corresponding hydroxy alkoxy 72.6 dyn / cm leads only slightly to about 59 to 70 dyn / cm 25 derivatives.

lower, result in the sucrose esters of substi- Another group of starting substances for

tuted stearic acids with at least one hydroxyl production of the sucrose esters according to the invention

group in the chain in a comparable concentration are unsaturated fatty acids, theirs from natural

a lowering of the surface tension of the fats obtained mixtures and the corresponding

Water to 30 to 35 dynes / cm. You can use it to reach the 30 lower alkyl esters. For example oleic acid,

Effect of normal soap and are more effective than ricinoleic acid, linolenic acid, soybean oil fatty acid and

Tetrapropylene benzene sulfonate, called the surface palm oil fatty acid. Proceeding from this

voltage is reduced to 40 dynes / cm and biologically one by direct hydroxylation, for example with

is not degradable. diluted permanganate solution, after which in Presentes

The object of the invention is to provide a Ver- 35 i la Societe Chimique Memoires (1952), p. 324,

drive to create the production of sucrose-described process to vic.-dihydroxy fatty acids

esters of substituted stearic acids with at least or their. Esters. An accumulation of water on the

allows a hydroxyl group in the chain, the double bond is conveniently made on the way

through the normal bacteria of the soil and the sulfurization with cold concentrated sulfur

Water can be completely broken down without acid (J. Am. Chem. Soc, 66 (1944), pp. 1924/1925)

this creates poisonous intermediate products, which the and subsequent hydrolysis with alcoholic caustic

Microflora of the soil or waterways damage alkali, which is easily obtained with the esterification of the

could. This object is achieved in that hydroxy fatty acid can be linked. In the same /

the initially known or known manner can be followed by a formoxylation after ^ Process prepared hydroxystearic acids or 45 the example in J. Am. Oil Chemist Soc, Dec.

whose lower alkyl esters with 1 to 4 carbon (1954), p. 3, described processes the double

atom.en in a known manner with sucrose binding of an unsaturated fatty acid in a hydroxyl

esterified or transesterified. Which are converted in this way and the hydroxy fatty acid

Nenen sucrose esters are solid, non-hygroscopic and can be directly esterified to sucrose ester. Through see, generally almost colorless substances, the direct oxidation of esters of unsaturated fatty acids

melt at temperatures below 65 ° C and therefore in with oxygen under UV irradiation one obtains the

the usual way, e.g. B. by spraying with corresponding hydroperoxydofatty acid ester (J. Am.

their known detergent ingredients, to Wasch-Chem. Soc, 71, pp. 282 to 286 [1949]). This attack

medium compositions can be processed. This takes place in the a-position to the double bond. The hydro

new sucrose esters show already at temperature peroxide can be converted to the corresponding unsaturated

Doors from 40 to 60 ° C optimal washing properties reduce alcohol and reduce it to the saturated

and are particularly suitable as detergents for hydrogenating hydroxy fatty acids. The addition of shark

delicate fabrics. genes, especially bromine, to unsaturated fatty acids,

It is most useful for the production of combined with subsequent alkaline saponification,

Sucrose esters according to the invention of known 60 is again a useful way to replace the or analogous processes are assumed in which the double bond has vicinal hydroxyl groups in the fatty hydroxystearic acids or to introduce their lower alkyl ester acid molecule (J. Org. Chem., 22, p. 319, with 1 to 4 carbon atoms produced synthetically 320 [1959]). Finally, one can from appropriate and then in a manner known per se with pipe-unsaturated hydroxy fatty acids or their lower ones sugar can be esterified or transesterified. Epoxyfett- 65 alkyl esters go out and the double bond after acids that hydrogenate into the above-mentioned hydroxyls the known methods of fat hardening, Stearic acids can be converted, or their thereby monohydroxystearic acids or their esters lower alkyl esters, in particular the methyl ester, arise, or according to one of the above-described

Replace methods with one or more other functional groups and in this way lead to hydroxy fatty acids or their derivatives arrive and then convert them to the desired sucrose esters.

The esterification of the naturally occurring or synthesized hydroxystearic acids or the transesterification of their esters with sucrose takes place in a strongly polar solvent. N-methylmorpholine, triethylamine, pyridine, quinoline, pyrazine, N-methylpyrazine, Ν, Ν'-dimethylpiperazine, 2-pyrrolidone, N-methylpyrrolidone are suitable. The best are N, N'-dimethylformamide and dimethyl sulfoxide. The esters are reacted with sugar using transesterification catalysts in a molar ratio of 1: 3. Catalysts are compounds with an alkaline reaction, in particular alkali metal hydroxides, such as potassium hydroxide or sodium hydroxide, potassium carbonate, potassium nitrate, potassium phosphate, sodium methylate, potassium ethylate, sodium saccharate and quaternary ammonium bases, such as alkyldimethylbenzylammonium hydroxide, alkyltrimethylammonium ammonium hydroxide, tetrahydroxydimethylammonium hydroxide, tetraalkyltrimethylammonium hydroxide. When using anhydrous sodium sulfide as the transesterification catalyst, particularly high yields are achieved. In order to promote the formation of sugar monoesters, it is advisable to use excess sugar and to work it up in a relatively strong dilution. The transesterification reaction takes place at temperatures between about 75 and 100 ° C. If the temperature is too high, the product can turn brown. In order to remove the split off lower alcohol from the reaction mixture, it is advisable to carry out the reaction under a weak vacuum of about 100 mm Hg. The alcohol formed can also be removed with an entrainer such as benzene at around 100 ° C without a vacuum. The reaction time is a few hours. After the transesterification has ended, the solvent ^{is stripped off at about 60 °} C. under reduced pressure. When using dimethylsulfoxide and dimethylformamide as solvents, it can be useful to add another suitable solvent after removing most of the solvent, in order to decompose the sugar esters by heating them for too long under vacuum, which is necessary to remove the last traces of dimethylsulfoxide or dimethylformamide would be to avoid. When using dimethylformamide, ketones such as acetone, methyl ethyl ketone, cyclohexanone, or esters such as ethyl or amyl acetate are suitable. If dimethyl sulfoxide is used, ketones and esters or aromatic hydrocarbons such as benzene are suitable. The residue or the precipitated product consists of a mixture of sugar esters and excess sugar. The excess sugar is first precipitated by treating with an extractant. Suitable for this are ketones, such as methyl isobutyl ketone, esters which contain at least 6 carbon atoms, such as amyl acetate, isobutyl acetate, and alcohols such as butanol. The Zuckerester containing the solution is then treated with a 5 to 10 ° / ₀ aqueous solution of sodium chloride, preferably at 40 to 80 ° C, washed to remove the last sugar moieties and the alkali metal salts of the fatty acid to be removed. The extraction can also take place continuously in a column in countercurrent. After removing the extractant, sugar ester remains in its pure form.

The table below shows the surface tension, the foaming power and the foam resistance and the immersion wetting power of the new substances and the corresponding values of known sugar esters, namely sucrose stearate and sucrose oleate, and known detergent raw materials, namely Marseille soap and tetrapropylbenzene sulfate, juxtaposed. The investigations were made with solutions of 1.5 g of the substance in distilled water. '

substance

Surface tension dynes / cm at 2O ⁰ C

Foaming power at 40 ⁰ C foam resistance at
40 ° C

1 minute

5 minutes I 10 minutes

Immersion wetting capacity at

40 ° C
Seconds

Marseille soap.

Tetrapropylbenzene sulfate

Sucrose oleate

Sucrose stearate, m.p .: 58 to 62 ° C sucrose-10-hydroxystearate,

M.p .: 57 to 59 ° C

Sucrose-12-hydroxystearate,

Mp: 58 to 62 ° C

Sucrose-10.n-dihydroxystearate,

M.p .: 52 to 53 ^° C

Sucrose-i ^ lO-dihydroxystearate,

M.p .: 45 to 55 ° C

Sucrose-9,10,12-trihydroxy-

stearate, m.p .: 50 to 59 ° C

Sucrose-12-hydroxy-9,10-epoxy-

stearate (semi-solid)

Sachcarose-9 (10) -hydroxy-10 (9) -

methoxystearate, m.p .: 48 to 55 ⁰ C sucrose-9 (10) -hydroxy-10 (9) -

prppoxystearate (semi-solid)

Sucrose-12,9 (10) -dihydroxy-10-

(9) methoxystearate, m.p .: 40 ° C sucrose-12,9 (10) -dihydroxy-10- (9) -propoxystearate (semi-solid) ...

29.4 33.3 55.4 65.4

37.7 31.0 33.7 34.4 35.4 37.2 34.4 36.2 35.8 37.2

100.0

84.8

3.9

• 3.1

24.3 11.5 24.8 20.3 14.8 17.4 36.9 15.8 29.1 32.1 100
100
100
100

100
100
100
100
100
100
100

100-

100
100

99.0
96.0
60.7
79.2

37.8
30.1
35.5
27.2
69.1
41.4
41.4
40.0
55.5
36.9

97.0
75.0
36.3
74.5

18.4
27.3
13.7
15.9
27.3
25.8
35.3
34.7
38.1
23.2

24
58
74
81

74
67
75
61
97
84
59
56
54
53

For example

Production of sucrose-lZ-hydroxystearate
from ricinoleic acid methyl ester

150 g Rizinolsäuremethylester were placed in a stirred autoclave 3.5 g of a 10 ° / ₀ by weight nickel catalyst on a kieselguhr support at temperatures of 140 ⁰ C and a pressure of 10 atmospheres with hydrogen hydrogenated. The reaction was over after about ¹ _1/2 hours. The solid reaction product was melted at 9O ⁰ C and filtered to remove the catalyst. Methyl 12-hydroxystearate with a melting point of 54 ° C. was obtained in almost quantitative yield. 53 g of this ester were then dissolved with 169 g of sucrose and 3.5 g of potassium carbonate in 650 ml of dimethylformamide and the reaction mixture was placed in a three-necked flask with constant stirring under nitrogen 8 cooked hours at 90 to 100 ⁰ C and about 100 mm Hg, until no methanol distilled over more. The dimethylformamide was evaporated and the residue dissolved in 500 ml of water at 50 until dissolved 6O ⁰ C and extracted with 300 ml of butanol. The butanol layer separated from the water was washed with a 5% saline solution. After the butanol had been distilled off, a white, solid, non-hygroscopic product remained. According to the analysis, it is sucrose-12-hydroxystearate (melting point: 56 ° C). The yield was .88% of theory.

30 Example 2

Manufacture of sucrose-10-hydroxystearate
from 9,10-epoxystearic acid methyl ester

.200 g of 9,10-epoxystearic acid methyl ester were dissolved in 500 ml of acetic acid, treated with 40 g of 5% palladium carbon and hydrogenated in an autoclave with hydrogen at room temperature and an initial pressure of 70 atm in about IV ₂ hours. The reaction product was poured into water, during which the 10-hydroxystearic acid methyl ester precipitated out as a white product. It was filtered off with suction, washed and dried and then has a melting point of 32 to 34 ° C. (VZ .: 194, theory 179). The yield was 95 ° / ₀ of the theory. 53 g of this 10-hydroxystearic acid methyl ester were transesterified to the sucrose ester in the manner described in Example 1, the 10-hydroxystearic acid methyl ester only being obtained in place of the 12-hydroxystearic acid methyl ester. Sucrose 10-hydroxystearate (melting point 57 to 59 ° C.) was obtained in a yield of 85% of theory.

Example3

Manufacture of sucrose-H-hydroxy- ^ lO-epoxystearate from ricinoleic acid methyl ester

100 g of ricinoleic acid methyl ester were stirred with 300 ml of Pere's acid solution (60%) at 20 to 25 ° C. for 3 hours. The reaction product was poured into 500 ml of water, resulting in a very good separation of the two phases. The oily layer was washed neutral with dilute sodium bicarbonate solution and dried with sodium sulfate. The yield of 12-hydroxy-9,10-epoxystearic acid methyl ester (n °% Found 1.4619) was 97 ° / ₀ of theory.

50 g of this ester were reacted with 156 g of sucrose and 1.5 g of anhydrous sodium sulfide in 650 ml of dimethylformamide in a three-necked flask with constant stirring under a nitrogen atmosphere at about 85 ° C. for 9 hours. The end of the reaction could be seen from the fact that no more methanol was distilled over. The dimethylformamide was then distilled off and the residue was dissolved in 500 ml of water at 50 to 60 ° C. and extracted with 300 ml of butanol. The butanol layer was washed with a 5% sodium chloride solution. After the butanol has been distilled off, a semi-solid, white product remains. According to analysis, it is sucrose-12-hydroxy-9,10-epoxystearate. The yield was 84 ° / ₀ of theory.

B e i s ρ i e 1 4

Production of sucrose lO.l ^ dihydroxystearate from 12-hydroxy-9,10-epoxystearic acid methyl ester

200 g of the prepared in Example 3 12-hydroxy-9,10-epoxystearinsäuremethylesters were oig ^he g Raney nickel is hydrogenated with 20 g of 5 ° / palladium-carbon and 10 in 500 ml of acetic acid in an autoclave at a hydrogen pressure of 70 atm at room temperature. After about ¹ _1/2 hours the reaction product became. poured into water, the 10,12-dihydroxystearic acid methyl ester precipitated out as a white product. This was filtered off with suction, washed and dried. The yield of the pure ester (melting point: 38 to 41 ^° C.; VZ: found 175, theoretically 170.5) • was 94%.

As described in the preceding example, the 10,12-dihydroxystearic acid methyl ester obtained is reacted with sucrose, only methyl 10,12-dihydroxystearic acid being used in place of the 12-hydroxy-9,10-epoxystearic acid methyl ester. Sucrose-10,12-dihydroxystearate (m.p .: 50 to 53 ° C) is obtained in a yield of 86 ° / ₀ of theory.

Example 5

Manufacture of sucrose 10 (9) hydroxystearate
by formoxylation

A mixture of 100 g of oleic acid, 200 ml of anhydrous formic acid and 1 ml of aqueous perchloric acid was refluxed under nitrogen for 15 minutes. The excess formic acid was then distilled off from the homogeneous solution (43 to 49 ° C./100 mm Hg). The residual crude Formoxystearinsäure was boiled for 15 minutes with a 100 ° / ₀ by weight excess of 6 η sodium hydroxide solution and optionally the still hot solution slowly with stirring into excess η 6-hydrochloric acid. On cooling, the upper layer solidified and could easily be separated from the water. Treatment with hot water, solidification, separation and drying gave a crude 10 (9) -hydroxystearic acid in a yield of about 80%. It could be further purified by recrystallization from low-boiling petroleum ether at room temperature and then had a melting point above 70 ° C.

The crude hydroxystearic acid was esterified in excess methanol with the introduction of dry hydrochloric acid gas for 4 to 5 hours and then the unused methanol was distilled off in a thin-film evaporator. The residue was washed with water and extracted with petroleum ether (bp .: 50 to 75 ⁰ C). After crystallizing out and. Development

fernüng of the solvent, the pure 10 (9) -Hydroxystearirisäuremethylester (m.p .: 32 to 34 ° C; VZ .: 189, in theory 179) in a yield of about 70 ° / ₀ of theory.

The ester is in the same way as described in Example 2, with sucrose to sucrose-10 (9) -hydroxystearate interesterified.

B e i s ρ i e 1 6

Production of sucrose-9,10-dihydroxystearate from oleic acid

720 ml of glacial acetic acid were heated ^{to 80 to 85 °} C. with 225 g of 30% strength hydrogen peroxide for 1 hour. The solution was cooled to 20 ° C. and 280 g of oleic acid were added. With stirring, the temperature rose slowly to 60 ^° C. The reaction mixture was filtered off and 2 l of water were then added. The aqueous solution was separated off, and the oily layer was boiled with 1800 ml of n-NaOH. The hot solution was acidified with η-hydrochloric acid and cooled. The precipitate in this way was separated off, washed with hot water, dried and recrystallized from alcohol. It was 9,10-Dihydroxystearinsäüre (m.p .: 89 ⁰ C) of the theory in a yield of 82 ° / _0th

The 9,10-dihydroxystearic acid was then esterified as in excess methanol with introduction of dry hydrochloric acid gas for 4 to 5 hours and then the unused methanol was distilled off in a thin-film evaporator. The residue was washed with water and extracted with Petroiäther 3 "· (Kp .: 50 to 75 ⁰ C). The 9,10-dihydroxystearate crystallized out, was filtered off and dried. The yield of pure product (m.p .: 65 ⁰ C ) was 80% of theory.

The methyl 9,10-dihydroxystearate was then transesterified with sucrose to give sucrose-9,10-dihydroxystearate, as described in Example 3 for methyl 12-hydroxy-9,10-epoxystearate. The yield of sucrose-9,10-dihydroxystearate (melting point: 45 to 55 ^° C.) was 86% of the 4 <> theory.

Example 7

Manufacture of sucrose-9,10-dihydroxystearate
by hydroxylation

1 kg of oleic acid was dissolved in 8 liters of a 2.5% strength aqueous soda solution on a water bath as sodium salt, then cooled and 2 kg of ice were added. At 10 ⁰ C of a 10% solution of potassium permanganate were trains sets, with vigorous stirring, the one hundred and first After stirring for a further 5 minutes, the solution was decolorized by introducing sulfur dioxide and the dihydroxystearic acid was precipitated by adding 11% of concentrated hydrochloric acid. The precipitated dihydroxystearic acid was filtered off with suction, washed with water and dried. The yield of 9,10-dihydroxystearic acid (melting point: 89 ° C.) was 75% of theory. In the same way as described in Example 6, this acid was esterified with methanol and the 9,10-dihydroxystearic acid methyl ester obtained was transesterified with sucrose to give sucrose-9,10-dihydroxystearate.

Examples

Production of sucrose-10-hydroxystearate : ■ · ■■. ■ from oleic acid

oleic acid was sulfurized sulfuric acid at 10 ⁰ C with three times the molar amount of 95%. According to hydro

45 lysis with excess methanolic KOH solution was acidified with a little concentrated sulfuric acid and refluxed for 2 hours. The yield of the mixture of oleic acid methyl ester and 10-hydroxystearic acid methyl ester was about 83%. About 50% of the methyl hydroxystearate was contained in the mixture. It was obtained in pure form by fractionation in vacuo (170 ° C./0.2 mm Hg) and transesterified with sucrose to give sucrose-10-hydroxystearate in the same way as described in Example 2.

Example 9

Production of sucrose-9,10-dihydroxystearate from 9,10-dibromostearic acid

A solution of 28.2 g of pure oleic acid and 0.28 g of di-tert-butyl-p-cresol in 200 ml of carbon tetrachloride was heated to boiling under nitrogen in order to drive off traces of moisture from the reactants and the apparatus. After cooling to ⁰ ° C., 16 g of dry bromine were added dropwise over the course of 30 minutes. Rapid discoloration occurred by the time about 90% of the bromine was added. After all of the bromine had been added, the solution was stirred for a further 30 minutes at 0 ° C. and then the still colored solution was decolorized by shaking with aqueous sodium bisulfite solution, washed with water and dried over anhydrous sodium sulfate. The freed of solvents product (44.5 g) was dissolved in 450 ml of acetone and stirred for 75 minutes at -20 ⁰ C. The precipitate was filtered off; after removal of the solvent from the filtrate, 43.3 g (98%) of pure 9,10-dibromostearic acid remained as a viscous brown oil. The 9,10-dibromostearic acid was hydrolyzed with excess methanolic KOH to give the potassium salt of 9,10-dihydroxystearic acid, this was converted into the free acid by acidification and esterified with small amounts of excess sulfuric acid to give 9,10-dihydroxystearic acid methyl ester, as described in Example 6 . The 9,10-dihydroxystearic acid methyl ester obtained in this way was transesterified according to Example 6 with excess sucrose to give sucrose-9,10-stearate.

Example 10

Production of sucrose-9,10,12-trihydroxystearate from 12-hydroxy-9,10-epoxystearic acid methyl ester

230 g of the 12-hydroxy-9,10-epoxystearic acid methyl ester (see Example 3) were heated to boiling with 1800 ml of In-NaOH, the hot solution was acidified with 6N hydrochloric acid and cooled. The precipitate was separated, washed with hot water, dried, "and recrystallized from alcohol. The yield of the 9,10,12-Trihydroxystearinsäuremethylester (m.p .: 73 ⁰ C) was about 80%.

50 g of the ester obtained were kept at 85 ° C. for 8 hours with 150 g of sucrose and 1.5 g of potassium carbonate in 600 ml of dimethylformamide and the methanol which had been split off was removed under a vacuum of about 100 mm Hg. Then, the dimethylformamide was distilled off in vacuo, the residue taken up in 500 ml water at 6O ⁰ C and extracted with 300 ml of butanol. The butanol extract was washed with a 5% NaCl solution. After the butanol had been distilled off, a white, solid, non-hygroscopic product remained which was after

209 623/67

single recrystallization in alcohol showed a melting point of 50 to 59 ° C, and this is due to was found to be sucrose 9,10-12-trihydroxystearate by analysis. The yield was 85%.

Example 11
Production of sucrose-II (8) -hydroxystearate by

Direct oxidation

In a flask connected to an oxygen bottle, 200 g of methyl oleate was placed Oxidized for 24 hours at 35 ° C under ultraviolet radiation. In this way, a total of 4570 g of methyl oleate was obtained implemented. The unreacted oleic acid ester is recrystallized twice separated from the mixture containing hydroperoxydooleic acid from a 10% solution in acetone. 158 g of an oil are obtained from the acetone solution, approximately 70% of which consists of methyl hydroperoxydooleate consists. This oil was in an aqueous methanol solution of sodium sulfite at a Temperature of about 70 ° C added dropwise with reflux cooling, the hydroperoxy group to the hydroxyl group is reduced. After the addition had ended, stirring was continued for about half an hour and then the oily phase is separated from the aqueous sodium sulfate solution after cooling.

R • OOH + Na ₂ SO ₃ -> R • OH + Na ₂ SO ₄

The obtained mixture of II (8) -hydroxyoleic acid methyl ester and oleic acid methyl ester was, as stated in Example 1, catalytically hydrogenated. The in almost quantitative yield obtained ll (8) -hydroxystearic acid methyl ester was in the same way, as in Example 1 for methyl 12-hydroxystearate described, converted into the sucrose ester.

B e i s ρ i e 1 12

Production of sucrose-9 (10) -hydroxy-10 (9) -methoxystearate from epoxystearic acid

.40

100 g of epoxystearic acid (95%), 300 g of absolute methanol and 1 g of sulfuric acid (96%) were Heated under reflux for 2 hours. 1.7 g of sodium hydrogen carbonate were then added to the solution Methanol is distilled off and the residue is dried with sodium sulfate.

The yield of 9 (10) -hydroxy-10 (9) -methoxystearic acid methyl ester was 81% of theory.

Calculation index nl °; 1.4508 found 1.4501 (theoretical).

47 g of the methyl ester were mixed with 150 g of sucrose and 1.5 g of potassium carbonate in 600 ml of dimethylformamide reacted under a vacuum of 100 nm Hg for 8 hours at 8 5 ° C and the split off methanol constantly removed. After distilling off the dimethylformamide in vacuo, the residue was in Poured 500 ml of water, extracted with butanol and distilled off the butanol from the extract. The received Product is almost colorless and has a soapy feel. The yield of sucrose-9 (10) -hydroxy-10 (9) -methoxystearate (Mp .: 48 to 55 ° C) was 80% of theory.

B e i s ρ i e 1 13

Production of sucrose-9 (10) -hydroxy-10 (9) n-propoxystearate from epoxystearic acid

Example 12 was repeated with the difference that n-propanol was used instead of methanol. 9 (10-hydroxy-10 (9) n-propoxystearinsäurepropylester was obtained in a yield of theory von'80 ° / _0th

Bp .: _{1> 5} = 220 ° C, nl °: 1.4497 found 1.4490 (theoretical).

This ester was, as in Example 12 9 _(10-Hy: described droxy-10 (9) -methoxystearinsäuremethylester transesterified with sucrose and sucrose-9 (10) -hydroxy-10 (9) n-propoxystearat as a semi-solid product in obtain a yield of 85 ° / ₀ of theory.

C found = 57.95%, theoretical 58.1%,
H found = 8.92%, theoretical 9.1%.

»5 B e i s ρ i e 1 14

Production of sucrose-12,9 (10) -dihydroxy-

10 (9) methoxystearate from epoxyrizinoleic acid

methyl ester

200 g of methyl epoxyrizinoleate (see Example 1) were refluxed with 800 g of methanol and 1 g of sulfuric acid (96%) for 2 hours. After adding the equivalent amount of NaHCO ₃ , the alcohol was distilled off, the residue was filtered and the oil obtained was distilled under vacuum:

1 Kp _{2 4} = 200 to 210 ° C. τι? = 1.4649

2nd bp, / ₄ = 210 to 220 ° C; riS = 1.4652

. The yield of 12,9 (10) -dihydroxy-10 (9) -methoxystearic acid methyl ester was 82%.

50 g of this ester were transesterified with 150 g of sucrose and 1 g of potassium carbonate in 650 ml of dimethylformamide. The reaction temperature was 85 ° C. and the reaction time was 9 hours. After distilling off the Dimethylformamide at about 60 ° C in vacuo, the residue was dissolved in water and, after the addition of. about 5% sodium chloride extracted with n-butanol. The butanol phase was washed once and that Butanol distilled off in vacuo. Sucrose-12,9- (10) -dihydroxy-10 (9) -methoxystearate was obtained as a solid white product with a melting point below 40 ° C. in a yield of almost 80% of theory.

Example 15

Preparation of sucrose-12,9 (10) -dihydroxy-10 (9) -n-propoxystearate from epoxyrizinoleic acid methyl ester

Example 14 was repeated with the difference that n-propanol was used instead of methanol would. The following fractions were collected during fractionation:

Kp.

1.5

150 to 160 ° C; n% ° = 1.4607
160 to 190 ⁰ C; n? = 1.4615
190 to 245 ⁰ C; n'i = 1.4620
245 to 250 ° C; /1? = 1.4648

The yield of 12,9 (10) -dihydroxy-10 (9) -n-propoxystearic acid propyl ester was 80%, based on the fractions.

Bp ₅ : 160 to 245 ° C.

This ester was instead of 12,9 (1O) -dihydroxy-10 (9) -methoxystearic acid methyl ester, as described in Example 14, transesterified with sucrose and sucrose-l ^ ilOJ-dihydroxy-lO ^ -n-propoxystearate obtained in a yield of 90% as a semi-solid product.

Claims (1)

11 12 Claim: can be established. net that one can initially search for known or, Process for the production of sucrose'- per se known processes produced hy- esters of substituted stearic acids with hydroxystearic acids or their lower alkyl esters At least one hydroxyl group in the chain, the 5 with 1 to 4 carbon atoms in per se known or sub-esterified or transesterified with sucrose by an epoxy or alkoxy group.