2-amino-2-deoxyglucose hydrochloride

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

実験手順: Glucosamine hydrochloride (50 g, 231 mmol) was suspended in anhydrous methanol (500 mL), then 2-acetyl-dimedone sodium salt (47.3 g, 231 mmol) was added. The reaction mixture was stirred at room temperature for 10 minutes, then 2-acetyl-dimedone (21.1 g, 115.9 mmol) was added. The reaction mixture was stirred under reflux for 2.5 hours and monitored by tlc. At the completion of the reaction (TLC: MeCN—H20, 10:2), the reaction mixture was cooled to room temperature and filtered. The filtrate was evaporated and the resulting solid residue was washed on a funnel with ether (3×500 mL) and dried to give crude product (75 g, 94%). No further purification was required for the next reaction. The reaction mixture was stirred under reflux for 2.5 hours the reaction mixture was cooled to room temperature filtered The filtrate was evaporated the resulting solid residue was washed on a funnel with ether (3×500 mL) dried

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

実験手順: Glucosamine hydrochloride ( 0.06 mol; 13.25 g), sodium carbonate (0.2 mol; 21.2 g) and sodium nitrite (0.2 g) were dissolved under nitrogen atmosphere at 0° C. in 100 ml of H2O. Methacryloyl chloride (0.12 mol; 13.0 g) was added under vigorous stirring. The reaction was carried out similar to the synthesis of 1 and gave the product as a white powder after two recrystallizations from water/ethanol/ether. Yield: 8.3-8.9 g (56-60%), p.m. (decomp.): 198°-199° C. The reaction was carried out similar to the synthesis of 1

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Glucosamine hydrochloride (0.1 mol; 21.56 g) and sodium nitrite (0.2 g) as inhibitor were dissolved under nitrogen atmosphere in 100 ml of a 0.3 M potassium carbonate solution, and the mixture was cooled to 0° C. Under vigorous stirring, acryloyl chloride (0.2 mol; 18.1 g) was added while the temperature was kept below 5° C. Stirring was continued for 3 h at 0°-5° C. and further 2 h while the mixture was allowed to come to room temperature. Finally, it was left at room temperature for 14 h. The solution was poured into 1 l of dry ethanol and strongly mixed. The resulting suspension was filtered by suction, and the cake was washed three times with 250 ml of 95% ethanol. To the combined filtrates and washings 1 l of ether was added and the solution was kept at 0° C. for 24 h. The desired product crystallized as white cubes, while the yellowish needles that might appear were a by-product. It could be separated by stirring up the whole mixture and decanting the liquid with the floating needles while the product remained on the ground of the reaction flask. By addition of 1 l of ether to the mother liquid a second crop could be isolated. The product was recrystallized two times from water/ethanol/ether. Yield 8.1-10.5 g (35-45%), m.p.:124°-125° C. was kept below 5° C to come to room temperature Finally, it was left at room temperature for 14 h strongly mixed The resulting suspension was filtered by suction the cake was washed three times with 250 ml of 95% ethanol To the combined filtrates and washings 1 l of ether was added the solution was kept at 0° C. for 24 h The desired product crystallized as white cubes, while the yellowish needles that It could be separated by stirring up the whole mixture decanting the liquid with the floating needles while the product By addition of 1 l of ether to the mother liquid a second crop could be isolated The product was recrystallized two times from water/ethanol/ether

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

実験手順: A mixture of 2.0 g of glucosamine hydrochloride, 5 ml of methanol and 5 ml of hydrazine hydrate was stirred overnight and then evaporated to dryness giving 2-amino-2-deoxy-D-glucose hydrazone. evaporated to dryness

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

実験手順: A mixture of 2.0 g of glucosamine hydrochloride, 5 ml of methanol and 5 ml of hydrazine hydrate was stirred overnight and then evaporated to dryness giving 2-amino-2-deoxy-D-glucose hydrazone. evaporated to dryness

反応条件: temp:4.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 20 g of glucosamine hydrochloride, 20 ml of glacial acetic acid, 80 ml of water and 9.1 ml of phenylhydrazine was heated on a steam bath for one hour, then cooled and filtered. The filtrate was hydrogenated in a Parr apparatus with Raney nickel catalyst until the uptake of hydrogen ceased. This mixture was then filtered, the filtrate was treated with activated charcoal and refiltered through diatomaceous earth, giving a green solution. A 6.31 ml portion of this green solution was treated with 0.24 g of sodium bicarbonate and a suspension of 1.66 g of potassium tetrachloroplatinate in 8 ml of water. The resulting reddish brown solution was stirred overnight, then cooled to 4° C. for 3 hours and the resulting solid collected. A 100 mg portion of this solid was stirred with 15 ml of hot water and then filtered through diatomaceous earth. The filtrate was cooled giving a solid which was collected, giving 90 mg of 1,2-diamino-1,2-dideoxy-D-glucitol, compound with platinum chloride (1:1) as yellow grains, mp 265° C. (dec.). cooled filtered This mixture was then filtered the filtrate was treated with activated charcoal giving a green solution the resulting solid collected A 100 mg portion of this solid was stirred with 15 ml of hot water filtered through diatomaceous earth The filtrate was cooled giving a solid which was collected

反応条件: temp:4.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 20 g of glucosamine hydrochloride, 20 ml of glacial acetic acid, 80 ml of water and 9.1 ml of phenylhydrazine was heated on a steam bath for one hour, then cooled and filtered. The filtrate was hydrogenated in a Parr apparatus with Raney nickel catalyst until the uptake of hydrogen ceased. This mixture was then filtered, the filtrate was treated with activated charcoal and refiltered through diatomaceous earth, giving a green solution. A 6.31 ml portion of this green solution was treated with 0.24 g of sodium bicarbonate and a suspension of 1.66 g of potassium tetrachloroplatinate in 8 ml of water. The resulting reddish brown solution was stirred overnight, then cooled to 4° C. for 3 hours and the resulting solid collected. A 100 mg portion of this solid was stirred with 15 ml of hot water and then filtered through diatomaceous earth. The filtrate was cooled giving a solid which was collected, giving 90 mg of 1,2-diamino-1,2-dideoxy-D-glucitol, compound with platinum chloride (1:1) as yellow grains, mp 265° C. (dec.). cooled filtered This mixture was then filtered the filtrate was treated with activated charcoal giving a green solution the resulting solid collected A 100 mg portion of this solid was stirred with 15 ml of hot water filtered through diatomaceous earth The filtrate was cooled giving a solid which was collected

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

実験手順: Reactions of carboxymethyl cellulose sodium salt (0.5-1.0% w/v) were carried out with glucosamine-hydrochloride (1.5-3.0% w/v) in the presence of equimolar amounts of base, such as a sodium bicarbonate solution (0.55-1.1% w/v) to neutralize the hydrochloride, sodium cyanoborohydride as reducing reagent (0.27-0.50% w/v), at room temperature, producing 2-amino-2-deoxy-glucose derivatives of carboxymethyl cellulose with nitrogen incorporation values of 2.60-3.07%, as shown in Table 2, page 17.

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

実験手順: contacting glucosamine hydrochloride with a sulfate of said metal in the presence of water to form an aqueous solution of glucosamine sulfate metal chloride; and

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

実験手順: contacting glucosamine hydrochloride with a sulfate of said metal in the presence of water to form an aqueous solution of glucosamine sulfate metal chloride; and

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

実験手順: Example 1 was repeated using 450 g of purified water, 107.8 g (0.5 mole) of glucosamine hydrochloride and 42.3 g (0.25 mole) of manganese sulfate monohydrate instead of the sodium sulfate. After freeze drying, glucosamine sulfate manganese chloride was obtained as a white powder in a yield of 144 g (98% of theoretical). After freeze drying

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

実験手順: Example 1 was repeated using 1679 g of purified water, 431.5 g (2 moles) of glucosamine hydrochloride and 128 g (1 mole) of lithium sulfate (monohydrate) instead of the sodium sulfate. After freeze drying, glucosamine sulfate lithium chloride was obtained as a white powder in a yield of 525 g (97% of theoretical). After freeze drying