Synthesis of Formose and Application

1.在N，N-二甲基甲酰胺（DMF）中，2-二甲氨基乙醇和盐酸硫胺催化的甲醛糖反应中，在甲醛浓度分别为1.1M和3.0M时，选择性地生成二羟基丙酮和DL-甘油四果糖。此外，通过调节DMF中水的含量，有利于2，4-二羟甲基-3-戊酮糖（2，4-BH-3-p）或2，4-BH-3-P的前体2-羟甲基-3-戊酮糖（2-H-3-P）的生成。这些产物也是从formose中分离出来的。以1，2，3，4-四-O-乙酰基-D-阿拉伯糖和甲醛为原料，在无水乙醇中与三乙胺和3-乙基-溴苯并噻唑（EBB）进行偶姻缩合反应，得到了一种新的碳链延长方法，收率较高。此外，甲醛糖反应是在各种无机碱的存在下，在Co-60 -射线的照射下，在甲醛水溶液中进行的。研究了甲醛浓度对产物的影响.由甲醛和各种金属-乙酰丙酮配合物选择性地合成了丙酮的多羟甲基化化合物。研究了不同金属-二胺配合物催化的糖异构化反应。Ni^2+、Co^2+、Ca^2+和Sr^2+能有效地催化醛糖C-2位的差向异构化反应。在Ca^<2+>的情况下，除了C-2差向异构体外，还形成了果糖.当福尔摩糖将被用于生物学时，可以预测非天然糖将影响生命功能。从这一角度出发，研究了不同微生物对非天然糖的分解和合成，并提出了其机理.对甲醛糖的酶法分析过程、糖的氧化过程以及糖的合成方法进行了研究。

1. In the formose reaction catalyzed by 2-(dimethylamino)ethanol and thiamin hydrochloride in N,N-dimethylformamide (DMF), dihydroxyacetone and DL-glycero-tetrulose were formed selectively at the formaldehyde concentration of 1.1 M and 3.0 M, respectively. Furthermore, the favored formation of 2,4- bis(hydroxymethyl)-3-&entulose(2,4-BH-3-p) or 2-hydroxymethyl-3-pentulose(2-H-3-P) which was a precursor of 2,4-BH-3-P, was obtained by regulating the fraction of water in DMF. Those products were also isolated from formose.2. A new carbon-chain lengthening method in carbohydrate synthesis of applying a selective acyloin condensation with triethylamine and 3-ethyl-bromobenzothiazolium(EBB) in ethanol was found to give d-fructose from 1,2,3,4-tetra-0-acetyl-D-arabinose and formaldehyde in a good yield. The formose reaction, furthermore, was carried out under the irradiation of Co-60 -ray to an aqueous formaldehyde solution in the presence of various inorganic bases. The effects of the formaldehyde concentration on products were also investigated.3. polyhydroxymethylated compounds of acetone were synthesized selectively from formaldehyde and various metal-acetylacetone complexes. Isomerization of sugars catalyzed by various metal-diamine complexes was studied. Ni^<2+>, Co^<2+>, Ca^<2+> and Sr^<2+> catalyzed effectively the epimerization at C-2 of aldoses. In the case of Ca^<2+>, fructose was formed besides the C-2 epimer.4. When formose will be used biologically, it might be predicted that non-natural sugars would affect vital functions. From these point of view, the decomposition and synthesis of non-natural sugars with various microorganizms were studied and their mechanisms were proposed.5. Analytical process of formose with enzymes, oxidation of sugars, and some approaches for synthesis of sugars have also been investigated.