Synthesis of Formose and Application

1. 在N，N-二甲基甲酰胺（DMF）中，2-（二甲氨基）乙醇和盐酸硫胺素催化福尔摩斯反应，在甲醛浓度为1.1 M和3.0 M时，选择性地生成了二羟丙酮和dl -甘油四糖。此外，通过调节DMF中水分的比例，得到了2,4-双（羟甲基）-3-和戊糖（2,4- bh -3-p）或2-羟甲基-3-戊糖（2- h -3-p）的有利生成。这些产物也是从台湾分离出来的。发现了一种碳链延长碳水化合物合成的新方法，即丙基糖与三乙胺和3-乙基溴苯并噻唑（EBB）在乙醇中选择性缩合，以1,2,3,4-四-0-乙酰- d-阿拉伯糖和甲醛为原料合成d-果糖，收率较高。此外，在Co-60射线照射下，在各种无机碱存在的甲醛水溶液中进行了福尔摩斯反应。考察了甲醛浓度对产品质量的影响。以甲醛和各种金属-乙酰丙酮配合物为原料，选择性地合成了丙酮的多羟基甲基化化合物。研究了不同金属-二胺配合物催化糖的异构化反应。Ni^<2+>, Co^<2+>, Ca^<2+>和Sr^<2+>有效地催化醛糖在C-2的外聚化。在Ca^<2+>的情况下，除了C-2外，还形成了果糖。当formose被生物利用时，可以预见非天然糖将会影响生命功能。从这些角度出发，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。对福尔摩糖的酶法分析过程、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.