(2R,3R,4R,5S)-6-aminohexane-1,2,3,4,5-pentol

反応条件: temp:-3.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 20 g 1-amino-1-deoxyglucitol (1a) are dissolved according to the method of Klein et al. (S. Engelke, Thesis, TU Braunschweig, FRG (1989)) in 100 ml water and cooled to -3° C. At this temperature 10 g isocyanatoethyl-methylacrylate (IEM, Dow Chemical) are added dropwise while stirring vigorously and during which the inner temperature is kept below 50° C. After completion of the isocyanate addition it is stirred for 12 hours and heated to room temperature. During the reaction time the emulsion which forms becomes a clear colourless solution. Subsequently the aqueous solution is extracted with ether in order to remove traces of undissolved isocyanate. After lyophilizing the solution the crude product is dissolved in methanol and recrystallized from acetone/ether (yield 35.3 g 95%); melting point 93° C. N-ethylmethacrylato-N'-1-deoxymaltitol urea (2), N-methylacrylato-N'-1-deoxycellobiitol urea (3) as well as N-ethylmethacrylato-N'-1-deoxylactitol urea (4) are produced in a corresponding manner from the corresponding 1-amino-1-deoxy sugars. is kept below 50° C is stirred for 12 hours heated to room temperature Subsequently the aqueous solution is extracted with ether in order to remove traces of undissolved isocyanate is dissolved in methanol recrystallized from acetone/ether (yield 35.3 g 95%)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-Amino-1-deoxy-D-glucitol (0.16 mol; 29 g) and 0.2 g NaNO2 were dissolved under a nitrogen atmosphere at 0° C. in 100 ml of a 0.3M K2CO3 solution. Acryloyl chloride (0.32 mol; 28.96 g) was added under vigorous stirring. The reaction was carried out similar to the synthesis of 1. After addition of ether, white crystals and a yellow oil were formed. The crystals were separated and gave the product, while the oil was discharged. Stepwise addition of 2 l of ether to the mother liquid and storing it in the refrigerator gave more of the desired product. For further purification the crystals were recrystallized twice from water/ethanol/ether. Yield: 22.2 g (59%), m.p.: 125° C. The reaction was carried out similar to the synthesis of 1 a yellow oil were formed The crystals were separated gave the product

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Glucose (0.55 mol; 100 g) was dissolved in 500 ml of H2O, and 40 ml of an 80% hydrazinium hydrate solution (1 mol) were added. The mixture was stirred slowly for 14 h and filled into a high pressure autoclave. Freshly activated Raney nickel (20 g) was added and the mixture was hydrogenated for 3 h at 50° C. while stirring with about 1000 r.p.m. The autoclave was depressurized and the product-catalyst mixture was filtered. The blue filtrate was treated with diacetyldioxime (2,3-butanedionedioxime) to remove the dissolved nickel. The product was concentrated to a clear yellowish syrup and was crystallized in the refrigerator. The white crystals were filtered off and washed with MeOH. If necessary the product was purified using the oxalate method of J. W. Long, G. N. Bollenbach in "Methods of Carbohydrate Chemistry" ed. by R. L. Whistler and M. L. Wolfrom, Academic Press N.Y. 1963, Vol. 2, P. 79). Yield: 80 g ( 80%), m.p.: 127° C. filled into a high pressure autoclave the mixture was hydrogenated for 3 h at 50° C. while stirring with about 1000 the product-catalyst mixture was filtered The blue filtrate was treated with diacetyldioxime (2,3-butanedionedioxime) to remove the dissolved nickel The product was concentrated to a clear yellowish syrup was crystallized in the refrigerator The white crystals were filtered off washed with MeOH If necessary the product was purified

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 184 mg of cyanuric chloride, 543.5 mg of D-glucamine and 450 mg of potassium carbonate were stirred at room temperature in 10 ml of water for three days. The thus-obtained crude product was thereupon chromatographed on LiChroprep RP-18 silica gel with water and subsequently with water containing an increasing amount of methanol. The relevant fractions were lyophilized; N,N',N"-(1,3,5-triazine-2,4,6-triyl)-tris-(1-amino-1-desoxy-D-glucitol) was thus obtained as a colorless powder, MS: m/z 619.2 ([M+H]+). The thus-obtained crude product was thereupon chromatographed on LiChroprep RP-18 silica gel with water and subsequently with water containing an increasing amount of methanol

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Equimolar quantities of lactic acid and glucamine were mixed together. This mixture was then heated at 120° C. for 2 hours and the resulting water of reaction was continuously removed. The final product was a viscous, amber colored liquid. was continuously removed

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 14.5 g of D-glucamine in 120 ml of water was covered with a solution of 11.4 g of naphthalene-1,5-disulfonyl chloride in 300 ml of ethyl acetate. 80 ml of a 1.0N sodium hydroxide solution were added dropwise to the vigorously stirred mixture during 4 hours. After stirring at room temperature for 20 hours the aqueous phase was separated, washed once with 100 ml of ethyl acetate and concentrated at 50° C. on a rotary evaporator. The viscous residue was evaporated azeotropically three times with 50 ml of toluene each time, subsequently taken up in a solution of 300 ml of pyridine and 100 ml of acetic anhydride and heated to reflux for 8 hours. The reaction mixture was again concentrated to dryness and partitioned between water and ethyl acetate. The organic phase was washed with water and sodium hydrogen carbonate solution, dried over magnesium sulfate and evaporated. The residue was chromatographed on silica gel in hexane/ethyl acetate as the eluent. 5.6 g of the purified product were dissolved in 100 ml of methanol and treated with 2 mg of sodium. After stirring for 16 hours. the insoluble precipitate was filtered off. This was dried at 50° C. in a high vacuum and gave naphthalene-1,5-disulfonic acid bis-D-glucit-1-ylamide, MS: m/z 615 ([M+H]+); 637 ([M+Na]+). was separated washed once with 100 ml of ethyl acetate concentrated at 50° C. on a rotary evaporator The viscous residue was evaporated azeotropically three times with 50 ml of toluene each time heated to reflux for 8 hours The reaction mixture was again concentrated to dryness partitioned between water and ethyl acetate The organic phase was washed with water and sodium hydrogen carbonate solution dried over magnesium sulfate evaporated The residue was chromatographed on silica gel in hexane/ethyl acetate as the eluent 5.6 g of the purified product were dissolved in 100 ml of methanol treated with 2 mg of sodium After stirring for 16 hours the insoluble precipitate was filtered off This was dried at 50° C. in a high vacuum

反応条件: temp:-3.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 20 g 1-amino-1-deoxyglucitol (1a) are dissolved according to the method of Klein et al. (S. Engelke, Thesis, TU Braunschweig, FRG (1989)) in 100 ml water and cooled to -3° C. At this temperature 10 g isocyanatoethyl-methylacrylate (IEM, Dow Chemical) are added dropwise while stirring vigorously and during which the inner temperature is kept below 50° C. After completion of the isocyanate addition it is stirred for 12 hours and heated to room temperature. During the reaction time the emulsion which forms becomes a clear colourless solution. Subsequently the aqueous solution is extracted with ether in order to remove traces of undissolved isocyanate. After lyophilizing the solution the crude product is dissolved in methanol and recrystallized from acetone/ether (yield 35.3 g 95%); melting point 93° C. N-ethylmethacrylato-N'-1-deoxymaltitol urea (2), N-methylacrylato-N'-1-deoxycellobiitol urea (3) as well as N-ethylmethacrylato-N'-1-deoxylactitol urea (4) are produced in a corresponding manner from the corresponding 1-amino-1-deoxy sugars. is kept below 50° C is stirred for 12 hours heated to room temperature Subsequently the aqueous solution is extracted with ether in order to remove traces of undissolved isocyanate is dissolved in methanol recrystallized from acetone/ether (yield 35.3 g 95%)

反応条件: temp:-3.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 20 g 1-amino-1-deoxyglucitol (1a) are dissolved according to the method of Klein et al. (S. Engelke, Thesis, TU Braunschweig, FRG (1989)) in 100 ml water and cooled to -3° C. At this temperature 10 g isocyanatoethyl-methylacrylate (IEM, Dow Chemical) are added dropwise while stirring vigorously and during which the inner temperature is kept below 50° C. After completion of the isocyanate addition it is stirred for 12 hours and heated to room temperature. During the reaction time the emulsion which forms becomes a clear colourless solution. Subsequently the aqueous solution is extracted with ether in order to remove traces of undissolved isocyanate. After lyophilizing the solution the crude product is dissolved in methanol and recrystallized from acetone/ether (yield 35.3 g 95%); melting point 93° C. N-ethylmethacrylato-N'-1-deoxymaltitol urea (2), N-methylacrylato-N'-1-deoxycellobiitol urea (3) as well as N-ethylmethacrylato-N'-1-deoxylactitol urea (4) are produced in a corresponding manner from the corresponding 1-amino-1-deoxy sugars. is kept below 50° C is stirred for 12 hours heated to room temperature Subsequently the aqueous solution is extracted with ether in order to remove traces of undissolved isocyanate is dissolved in methanol recrystallized from acetone/ether (yield 35.3 g 95%)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-Amino-1-deoxy-D-glucitol (0.16 mol; 29 g) and 0.2 g NaNO2 were dissolved under a nitrogen atmosphere at 0° C. in 100 ml of a 0.3M K2CO3 solution. Acryloyl chloride (0.32 mol; 28.96 g) was added under vigorous stirring. The reaction was carried out similar to the synthesis of 1. After addition of ether, white crystals and a yellow oil were formed. The crystals were separated and gave the product, while the oil was discharged. Stepwise addition of 2 l of ether to the mother liquid and storing it in the refrigerator gave more of the desired product. For further purification the crystals were recrystallized twice from water/ethanol/ether. Yield: 22.2 g (59%), m.p.: 125° C. The reaction was carried out similar to the synthesis of 1 a yellow oil were formed The crystals were separated gave the product

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Glucose (0.55 mol; 100 g) was dissolved in 500 ml of H2O, and 40 ml of an 80% hydrazinium hydrate solution (1 mol) were added. The mixture was stirred slowly for 14 h and filled into a high pressure autoclave. Freshly activated Raney nickel (20 g) was added and the mixture was hydrogenated for 3 h at 50° C. while stirring with about 1000 r.p.m. The autoclave was depressurized and the product-catalyst mixture was filtered. The blue filtrate was treated with diacetyldioxime (2,3-butanedionedioxime) to remove the dissolved nickel. The product was concentrated to a clear yellowish syrup and was crystallized in the refrigerator. The white crystals were filtered off and washed with MeOH. If necessary the product was purified using the oxalate method of J. W. Long, G. N. Bollenbach in "Methods of Carbohydrate Chemistry" ed. by R. L. Whistler and M. L. Wolfrom, Academic Press N.Y. 1963, Vol. 2, P. 79). Yield: 80 g ( 80%), m.p.: 127° C. filled into a high pressure autoclave the mixture was hydrogenated for 3 h at 50° C. while stirring with about 1000 the product-catalyst mixture was filtered The blue filtrate was treated with diacetyldioxime (2,3-butanedionedioxime) to remove the dissolved nickel The product was concentrated to a clear yellowish syrup was crystallized in the refrigerator The white crystals were filtered off washed with MeOH If necessary the product was purified

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 184 mg of cyanuric chloride, 543.5 mg of D-glucamine and 450 mg of potassium carbonate were stirred at room temperature in 10 ml of water for three days. The thus-obtained crude product was thereupon chromatographed on LiChroprep RP-18 silica gel with water and subsequently with water containing an increasing amount of methanol. The relevant fractions were lyophilized; N,N',N"-(1,3,5-triazine-2,4,6-triyl)-tris-(1-amino-1-desoxy-D-glucitol) was thus obtained as a colorless powder, MS: m/z 619.2 ([M+H]+). The thus-obtained crude product was thereupon chromatographed on LiChroprep RP-18 silica gel with water and subsequently with water containing an increasing amount of methanol

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Equimolar quantities of lactic acid and glucamine were mixed together. This mixture was then heated at 120° C. for 2 hours and the resulting water of reaction was continuously removed. The final product was a viscous, amber colored liquid. was continuously removed