DE1261861B - Process for the production of glycamine capsules - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C07c

German class: 12 q- 32/01

Number: 1261 861

File number: D42304IVb / 12q

Filing date: August 22, 1963

Open date: February 29, 1968

It is already known that the reaction of water-soluble N-monoalkylated glycamines, the alkyl radicals of which contain 1 to 8 carbon atoms, with higher molecular weight fatty acid esters at temperatures between 140 and 230 ° C. leads to the corresponding N-acylation products which have surface-active properties. Reworking of this process at temperatures ίο währleisten overall sufficient for the technical implementation reaction rate in the specified frame, that is, at about 160 to 200 ⁰ C, showed that leads to dark-colored reaction products, the only hazy in water, dark solutions give . This is evidently due to the unavoidable formation of by-products and decomposition products occurring at the reaction temperature. When temperatures below 140 ^° C. are used, no reaction takes place even under reduced pressure.

Glycamines which are monoalkylated on the nitrogen and whose alkyl radicals contain 10 to 20 carbon atoms known and represent relatively poorly soluble products with a certain surface-active effect.

It has been found that glycamine derivatives of the general formula can be obtained

R - N

in which R denotes the sugar residue of glycamine, R ₁ denotes an alkyl group with 10 to 20 carbon atoms and R ₂ denotes an acyl group with 1 to 5 carbon atoms, which can be produced by corresponding N-monoalkylglycamines with corresponding carboxylic acids or theirs in a manner known per se reactive derivatives or ketene or its reactive derivatives at temperatures between 30 and 150 ⁰ C converts.

The products obtained surprisingly show signs of resistance compared to the monoalkylated glycamines a significantly improved solubility and, at the same time, a significantly increased surface activity on. In addition, these are new types produced by the method used according to the invention Products are almost colorless and clear at the permissible low conversion temperatures Solutions, i.e. without the formation of disruptive by-products.

Suitable N-alkyl-glycamine are in a known manner by catalytic hydrogenation of mixtures for the preparation of
Glycamine derivatives

Applicant:

Dehydag Deutsche Hydrierwerke G. m. B. H.,

4000 Düsseldorf, Henkelstr. 67

Named as inventor:

Dr. Arnold Heins, 4010 Hilden

from monosaccharides such as glucose, mannose, galactose, fructose and sorbose or mixtures of monosaccharides, such as those found in invert sugar, and N-alkylamines with a hydrocarbon chain obtained from 10 to 20 carbon atoms. The hydrocarbon chains can also interrupted by O, S and N or corresponding atom groupings or by containing these atoms Groups may be substituted.

For practical reasons, acetic anhydride is predominantly used as the acylating agent, but are also other low molecular weight carboxylic acids, their anhydrides, halides or esters in the same way suitable. Furthermore, ketene and its derivatives, such as isopropenyl acetate, proven.

The reaction of the invention takes place at temperatures of 30 to 145 ° C, preferably at 30 to 100 ⁰ C, depending on reactivity of the starting materials, components, optionally in the presence of inert solvents, with or without pressure. The N-acyl-N-alkyl-glycamines prepared according to the invention are pasty or solid and have excellent wetting and dispersing properties.

Examples

The table below shows the data for various N-acetyl-N-alkyl-glycamines obtainable according to the invention which are obtained in the following manner.

1 mole of N-alkyl-glycamine was dissolved in around 1550 to 2000 ml of glacial acetic acid. Then 1.05 mol of acetic anhydride was added dropwise at 45 ^{° C. with stirring.} After the addition of the acylating agent, the solution was ^{heated to 90 °} C. for 1/2 hour. then

809 510/341

the excess acetic anhydride and the acetic acid were distilled off at 90 to 100 ^{° C. in a water jet vacuum.} The corresponding N-acetyl-N-alkyl-glycamide was obtained in pure form. The faint odor of acetic acid that might still cling to the product could be removed by drying over sodium hydroxide. The products dissolve, if necessary with slight warming, in water and all polar organic solvents.

Tabel

N-alkyl-glycamine sugar Alkyl radical R Acylating agents yield N-Acy I-N-alkyl-glycamkl surfaces tension example
TvIi- glucose C ₁₂ H ₂₃ ( ¹ Vo) Melting point (0.1 eat water Nk glucose C ₁₄ H ₂₉ Acetic anhydride 97 23 ± 1-C) glucose QoH ₃₃ Acetic anhydride 99.5 (-C) 29.7 dynes / cm 1 glucose C ₁₈ H ₃₇ Acetic anhydride 99.5 - 31.1 dynes / cm 2 Fructose C ₁₂ H ₂ S Acetic anhydride 98.5 - 32.1 dynes / cm 3 Galactose C ₁₂ H ₂₅ Acetic anhydride 91 34.5 46.6 dynes / cm 4th Invert sugar C ₁₂ H ₂₅ Acetic anhydride. 95 48.5 to 50 30.5 dynes / cm 5 Invert sugar QeH ₃₇ Acetic anhydride '96 - 30.9 dynes / cm 6th glucose (CH ₂ ) 3 OC ₁₂ H ₂₅ Acetic anhydride 97 - 30.1 dynes / cm 7th glucose (CH ₂ J ₃ OC ₁₄ H ₂₉ Acetic anhydride 97.5 - 47.5 dynes / cm 8th glucose - (CH ₂ J ₃ -OC ₁₆ H ₃₃ Acetic anhydride 99.5 - 31.7 dynes / cm 9 glucose - (CH ₂ J ₃ -OQ ₈ H ₃₇ Acetic anhydride 99 - 32.3 dynes / cm 10 Acetic anhydride 99.5 30th 33.9 dynes / cm 11 41 44.5 dynes / cm 12th 53 to 55

40

Example 13

30 g of N-dodecylglycamine were mixed with 7.05 g of methyl acetate. The mixture was heated ^{to 145 °} C. in an autoclave for 18 hours. The methanol formed was then stripped off in vacuo. Colorless, pasty N-acetyl-N-dodecylglycamine remained in a yield of 89.5% of theoretical. The surface tension of the product (0.1 g / l water at 23 ± 1 °) was 29.8.

Example 14

30 g of N-dodecylglycamine, suspended in 200 ml of anhydrous toluene, were admixed with 5.9 g of acetyl chloride at 60.degree. The mixture was then ^{heated to 110 °} C. for 40 hours and nitrogen was passed through in a slow stream in order to remove the hydrogen chloride formed in the acetylation. After the solvent had been stripped off in vacuo, 32 g (corresponding to 95.5% of theory) of colorless N-acetyl-N-dodecylglycamine were obtained. The surface tension of the product (0.1 g / l water at 23 ± 1 °) was 29.9.

Example 15

50 g of N-dodecylglycamine were mixed with 15.2 g of isopropenyl acetate offset. The mixture was then heated to 120 ° C. and over a 30 cm long packed column the acetone formed during the acylation is distilled off. After removing the last volatile components 48.3 g (86.3% of theory) of analytically pure N-acetyl-N-dodecylglycamine remained in the vacuum. The surface tension of the product (0.1 g / l water at 23 ± 1 °) was 29.7.

Example 16

50 g of N-dodecylglycamine were mixed with 29.4 g of 90% strength formic acid and refluxed for 3 hours. The excess formic acid was then ^{distilled off at 50 °} C. in vacuo and the last acid residues were removed from the residue using NaOH in vacuo. 49.5 g (corresponding to 92% of theory) of colorless N-formyl-N-dodecylglycamine remained. The substance dissolved very easily in water. The surface tension of the product (0.1 g / l water at 23 ± 1 °) was 30.5.

Example 17

50 g N-Hexadecylglycamin were with a mixture of 13.2 g of acetic anhydride and 11.4 g of 100% formic acid, first for 2 hours at 35 ° C, then heated to 110 ⁰ C for 2 hours. The volatile components were then from the reaction mixture at 8O ⁰ C distilled off in vacuo. The colorless N-formyl-N-hexydecylglycamine obtained in 95% of theoretical yield was readily soluble in water and showed a high surface activity. The surface tension of the product (0.1 g / l water at 23 ± 1 °) was 33.5.

Example 18

A mixture of 50 g of N-dodecylglycamine and 20.5 g of butyric acid n-propyl ester was so long under Stirring heated to 140 ° C. until 8.6 g of n-propanol had distilled off therefrom. 51.1 g of N-butyryl-N-dodecylglycamine remained back, which froze glassy when cooled. The surface tension of the product (0.1 g / l water at 23 ± 1 °) was 32.3.

Claims (1)

Claim: Process for the preparation of glycamine derivatives of the general formula R —N in the R the sugar residue of the glycine, R ₁ a Alkyl radical with 10 to 20 carbon atoms and R ₂ denotes an acyl radical with 1 to 5 carbon atoms, by acylation of N-monoalkylglycamines with carboxylic acids or their derivatives, characterized in that corresponding N-monoalkylglycamines with corresponding carboxylic acids or their reactive ones are used in a manner known per se Derivatives or ketene or its reactive derivatives at temperatures between 30 and 150 ⁰ C converts. When the application was announced, two sheets of comparison tests were laid out. 809 510/341 2.68 © Bundesdruckerei Berlin