CHEMICAL PATHWAYS FOR THE PREPARATION OF LABELED DERIVATIVES OF DIHYDROXYACETONE
The object of this investigation was to devise a chemical synthesis of dihydroxyacetone phosphate in a manner that could produce a product uniquely labeled at carbon atoms 1, 2, or 3. This compound would be useful for the enzymatic synthesis of D-fructose-1,6-diphosphate uniquely labeled with C/sup 14/ in any position, a specificity of labeling that has never been before achieved in hexoses. The synthesis was accomplished by treating chloroacetamide with sodium benzoate to prepare benzoylglycolamide. The amide was converted into the corresponding carboxylic acid and thence into acid chloride. The acid chloride was transformed into the diazoketone which upon reaction with ortho-phosphoric acid afforded 1-benzoxy3-hydroxypropanone. This intermediate was ketaiated with trimethyl orthoformate in methanolic hydrogen chloride and the alcohol group phosphorylated with diphenyl phosphorochloridate. The phenyl groups were removed by hydrogenolysis and the ester hydrolyzed with barium hydroxide. The dimethyl ketal of dihydroxyacetone phosphate was then isolated as its cyclohexyl ammonium salt. Starting with chloroacetamide, the dimethyl ketal of dihydroxyacetone phosphate was obtained in an overall yield of 26%. A similar synthesis was carried out from acetylglycolic acid and the dimethyl ketal of dihydroxyacetone phosphate was isolated in less than 0.1% overall yield. Attempts were made to use the key intermediate, 3-benzoxy-1-diazopropanone, to provide a shorter route to dihydroxyacetone phosphate. These attempts were unsuccessful. (Dissertation Abstr., XXIII, No. 12(1))
- Research Organization:
- Originating Research Org. not identified
- NSA Number:
- NSA-17-030608
- OSTI ID:
- 4684460
- Resource Relation:
- Other Information: Thesis. Orig. Receipt Date: 31-DEC-63
- Country of Publication:
- Country unknown/Code not available
- Language:
- English
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