DE1250808B - Process for the preparation of carbamic acid esters of aliphatic polyhydroxy compounds - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN 4W3Wl PATENT OFFICE

EDITORIAL

Int Cl

number
File number*
Filing date
Display day

C 07c

ClId

German class 12 ο -17/01

C07h

1 250 808
D46413IVb / 12o

February 2, 1965

28 September 1967

The invention relates to a method of manufacture nonionic, surface-active carbamic acid ester ahphatic polyhydroxy compounds

"As is known, carbamic acid esters can be aliphatic Polyhydroxy compounds by reacting the corresponding polyhydroxy compounds with higher molecular weight iscocyanates in dimethylformamide The implementation is special of sucrose with aliphatic long-chain isocyanates and the conversion of sugar alcohols with aliphatic isocyanates (H. Bertsch, E Ulsperger, W Gerhardt and M. Bock, J practice chemistry [4] Vol 11, 1960, p 108 up to 111)

The known preparation methods all work using alkyl isocyanates, these isocyanates However, they are difficult to access ζ B for the representation from paraffin, six levels of paraffin (paraffin oxidation) -> Fatty acid (reaction with ammonia) - »carboxylic acid (hydrogenation) - * ■ Fettanun (reaction with hydrochloric acid) -> Fettammhydrochlond (phosgenation) -> · fatty isocyanate

The object of the invention is not to isocyanate Established manufacturing process for carbamic acid esters to find aliphatic polyhydroxy compounds

The method of the invention is characterized in that one uses ahphatic polyhydroxy compounds with three to fifteen hydroxyl groups in the molecule, such as glycerol, erythritol, sorbitol, dulcitol, mannitol, pentaerythritol, dipentaerythritol, especially sugar and their derivatives, such as erythrose, glucose, galactose, mannose, reacting sucrose and raffinose, m with high molecular weight alkyl halides, especially chlorides and bromides, and alkali presence of dimethylformamide as solvent at temperatures from 60 to 153 ⁰ C.

The implementation takes place according to the formula scheme

R - Hai + KNCO + HO - R ₁ - * - R - NH-CO-O - Ri + KHaI

whereby N-alkyl-carbammic acid esters are formed

Undesired side reactions are caused by empirical Regulation of the molar ratios, the amount of solvent and the duration of the reaction either completely switched off or at least pushed back on a large scale

The compounds which can be prepared after learning the invention are urethanes of aliphatic polyhydroxy compounds, especially of sugars They can be used as a wetting agent and cleaning agent, Process for the production of carbamate esters of aliphatic polyhydroxy compounds

Applicant

German Academy of Sciences in Berlin, Berlm-Adlershof, Rudower Chaussee 5

Named as the inventor

Dipl-Chem Dr Werner Gerhardt,

Berlm-Adlershof

because they have good surface-active and detergent properties in addition to 100% bacteriological degradability and also hemolytic and cytolytic Possess effectiveness.

The advantage of the method of the invention consists in particular in the easier accessibility of the raw materials, ζ B of the alkyl halide by halogenation of petroleum fractions with a corresponding chain length and the alkali cyanate by melting potassium carbonate with urea

The following examples illustrate the process the invention

example 1

165.2 g (0.5 mol) of dried sucrose are dissolved in 11% of anhydrous dimethylformamide, and 40.5 g (0.5 mol) of potassium cyanate (or 32.5 g [0.5 mol] of sodium cyanate) and 3 g of triethylamm are added and let to 137.5 g (0.55 mol) dodecyl-1-bromide at about 90 ⁰ C with good stirring enter Man holding this temperature for about 2 hours, the reaction mixture is subsequently cooled to room temperature and filinert from the precipitated potassium bromide (or Sodium bromide) and Ν, Ν'-didodecylurea from The dimethylformamide is removed from the filtrate in vacuo. The remaining residue is taken up in 11% water and this solution is shaken twice with a mixture of butanolhexane drying is obtained 195 g (70% of theory) of a light yellow, very viscous syrup This is umknstallisiert from Essigester and yields 120 g (43% of theory) of colorless sucrose Nn-dodecylurethan (mixture of isomers) of melting point about 120 ⁰ C

709 649/453

Example 2

According to Example 1, 200 g (0.6 mol) of sucrose m 1000 ml of dimethylformymide in the presence of 3 g of methylamine with 40.5 g (0.5 mol) of potassium cyanate (or correspondingly 32.5 g [0.5 mol] of sodium cyanate ) and 133 g (0.5 mol) of an alkyl bromide mixture C ₁₀ to C ₁₆ reacted, reaction temperature 90 to 95 ° C., reaction time 3 hours

Example 4

According to Example 1, 91 g (0.5 mol) of mannitol are dissolved in hot dimethylformamide in the presence of 3 ml of methylamine with 20.3 g (0.25 mol) of potassium cyanate and 51.2 g (0.25 mol) of dodecyl chloride HO ⁰ C reaction temperature reacted within 2 hours and worked up as in Example 1 50 g (51% of theory) of mannitol-Nn-do-

as in Example 1 and obtained 277 g (98% of the io decyl urethane (mixture of isomers), from which

Theory) of a clear amber-colored resin which, after recrystallization from acetic acid, gives a colorless sucrose-Nn-alkyl urethane mixture (C _{10 -C 16} isomer mixture)

Example 3

200 g (0.6 mol) of sucrose are dissolved in 11% of anhydrous dimethylformamide at about 90 ° C., 3 g of methylamine, 40.5 g (0.5 mol) of potassium cyanate and 112 g (0.55 mol) of dodecyl chloride are added and the mixture is heated these ao mixture is about with stirring at 120 to 130 ⁰ C. Thereafter, operation is as in example 1. one obtains 141 g (51 ° / ₀ dei theory) of sucrose-Nn-dodecylurethan (isomer mixture) umkristalhsieit from Essigester, shows 2 ¹ \ hours it has a melting point of about 120 ^° C

mahges recrystallization from methanol 18 g (18% '
Be obtained theory) of needle-shaped crystals of melting point 150 ⁰ C (mannitol-1-Nn-dodecylurethan)

Claims (1)

Claim Process for the production of carbamate estersahphatischerPolyhydroxyverbindungen, characterized 'that one aliphatic polyhydroxy compounds with three to fifteen hydroxyl groups in the molecule, especially sugar and their derivatives, with high molecular weight alkyl halides, especially chlorides and bromides, and alkahcyanate in the presence of dimethylformamide as a solvent at temperatures from 60 to 153 ⁰ C converts 709 649 / 4S3 9 67 © Bundesdruckerei Berlin