碳水化合物之氧化反應　第二報　氧化蔗糖試製糖酸

Oxidation of Carbohydrates. II. Synthesis of Glucosaccharic Acid From Sucrose

賈魁士(Kuei-shih Chia) ； 林建中(Chen-chong Lin)

《化學》 51年3期 (1962/09) Pp. 98-104

https://doi.org/10.6623/chem.1962017

摘要

本試驗係利用臺省盛產之蔗糖、葡萄糖及澱粉為原料，藉硝酸氧化作用，試製糖酸。醣類生成糖酸之原理，基於分子結構中之葡萄糖分子之兩端被氧化，普通尚可得草酸為副產品，由實驗結果得知：(1)蔗糖60公克，加30%硝酸240公撮，在85°C下，反應15小時，得糖酸氫鉀鹽25.3%，草酸15.7%。(2)由葡萄糖、澱粉製造糖酸之條件，與蔗糖大致相同，惟以葡萄糖為原料時，反應時間可稍縮短，以澱粉為原料時，則反應時間須稍行延長。最佳產率，由葡萄糖得糖酸氫鉀鹽46.8%，草酸12.9%。由澱粉（蕃薯粉）得糖酸氫鉀鹽44.0%，草酸11.8%。(3)使用釩酸鈉為觸媒，可縮短反應時間及降低反應溫度，草酸產率雖略見增加，但糖酸產率並無顯著改變。(4)經採用新步驟，由葡萄糖100公克，加70%硝酸130公撮，另加亞硝酸鈉1公克，起溫度60-65°C下反應7小時，得糖酸氫鉀鹽56.3%，草酸5.6%。(5)各醣類依上述條件反應後，經提出糖酸氫鉀鹽及草酸後之殘液，所含糖份均不超過5%以上，明示反應接近完全。

並列摘要

Study has been made on the oxidation of sucrose with nitric acid to obtain glucosaccharic acid, which is generally regarded as a source of useful products. Glucose and starch are also chosen as raw materials in the experiment. When the oxidation is carried out under suitable conditions, the glucose portion of the molecule in these raw materials is converted into glucosaccharic acid, but oxalic acid is generally produced as by-product. Under the optimum condition, the yield with potassium hydrogen glucosaccharate is 25.3% from sucrose, 46.8% from glucose and 44.0% from starch, respectively. As for oxalic acid, the yield is 15.7% from sucrose, 12.9% from glucose arid 11.8% from starch respectively (see Fig. 1, 2, 3, 4, Table 2 and 3). All the calculations are based on the raw materials in dry state; When the reaction is catalyzed by the presence of sodium vanadate, the oxldation time required is shortened and the oxidation temperature is consequently decreased. Improved yield with oxalic acid by use of catalyst is obtained, but no marked effect on the yield of glucosaccharic acid is realized (see Table 1). However, when the improved procedure is adopted, a higher yield with potassium hydrogen glucosaccharate of 56.3.%' from glucose is obtained. This procedure is as follows: Dissolving 100g glucose in 40 ml H_2O, adding one-fifth of this solution to 130 ml 70% HNO_3 at 60°C, adding 1g NaNO_2 to initiate the reaction, the remaining glucose solution is added uniformly at 6G-65°C within one hour to the reaction mixture and then allowed to react for 6 hours. Cooling and adding aqueous KOH to pH 11.2, the mixture is then heated to 80°C for 0.5 hour. Cooling again and adding 70% HNO_2 to pH 3.4, then 56.3g of KH-ghrcosaccharate is precipitated. The reaction mechanism connected with these Observations is discussed.