Glycolaldehyde

Formaldehyde reacts with syn gas (CO,H2) to produce added value products. Ethylene glycol (EG) may be produced in a two-stage process or the intermediate, glycolaldehyde, isolated from the first stage (65) ... 

Other aldehydes which have been used in the reaction are pro-panal, butanal, glycolaldehyde, 3-hydroxybutanal, and a number of phenylacetaldehydeand benzaldehyde derivatives. Whereas condensation of tryptophan with acetaldehyde takes place even at room temperature and pH 6.7, the reactions with chloral, chloroacetaldehyde, and crotonaldehyde fail entirely. 

Other routes have been tried starting from formaldehyde or paraformaldehyde. One process reacts formaldehyde with carhon monoxide and H2 (hydroformylation) at approximately 4,000 psi and 110°C using a rhodium triphenyl phosphine catalyst with the intermediate formation of glycolaldehyde. Glycolaldehyde is then reduced to ethylene glycol ... 

Supplement 1941 1-161 Derivatives. Methyl alcohol, 273. Ethyl alcohol, 292. Ethyl ether, 314. Glycerol, 502. Carbonyl Compounds Aldehydes, Ketones, Ketencs and Derivatives. Formaldehyde, 558. Acetaldehyde, 635. Acetone, 635. Ketene, 724. Hydroxy-Carbonyl Compounds Aldehyde-Alcohols, Ketone-Alcohols, Monosaccharides and Derivatives. Glycolaldehyde, 817. Aldol, 824. Pentoses, 858. Hexoses, 878. 

The alkoxy radical OC2H4OH formed in the process either dissociates into CH20 and CH2OH, or reacts quickly with 02 to form glycolaldehyde (HOCH2CHO) and H02 H02 is also formed by the reactions of CHO and CH2OH with 02, and contributes as well to NO oxidation ... 

The addition of ethylene decreased notably the energy consumption for NO removal. Niessen [33] obtained energy costs of 61 eV/NO removed in the absence of ethylene and only 9.6 eV/NO removed when ethylene is present in the gas mixture. However, the NO concentration does not change much, as NO is mostly converted to NOz. The main reaction products obtained in the presence of ethylene are N02, glycolaldehyde (OC2H3OH), formaldehyde (CH20), and oxirane. 

Moreover, Kim and coworkers have shown that a-amino-butyrolactones can be synthesized by a related process employing the amino acid homoserine with an unprotected hydroxy functionality [31]. In a more recent publication by the same research group, morpholin-2-one derivatives of type 9-37 have been prepared (Scheme 9.6) [32]. Herein, glycolaldehyde dimer 9-32 acts as a bifunctional compound, which first reacts with the a-amino acids 9-33 to give the iminium ions 9-34,... 

Isobe, K. and Nishise, H. (1995) A new enzymic method for glycolaldehyde production from ethylene glycol. Journal of Molecular Catalysis B-Enzymatic, 1 (1), 37—43. 

As already shown in Sect. 4.4, ribose-2,4-diphosphate is obtained in a base-catalysed condensation of glycolaldehyde phosphate in the presence of formaldehyde (Muller et al., 1990). The phosphate group in the 4 position of the sugar prevents the formation of a 5-membered furanose ring, but a 6-membered pyranose structure can be formed. 

Arthur L. Weber (1998), now working at the Seti Institute of the Ames Research Center at Moffett Field, reports the successful synthesis of amino acid thioesters from formose substrates (formaldehyde and glycolaldehyde) and ammonia synthesis of alanine and homoserine was possible when thiol catalysts were added to the reaction mixture. On the basis of his experimental results, Weber (1998) suggests the process shown in Fig. 7.10 to be a general prebiotic route to amino acid thioesters. 

The reaction with ethyl acetoacetate has been extended to glycolaldehyde, and to carbohydrates other than n-glucose, by employing different experimental conditions it is probably applicable to aldoses in general. With d-fructose, yields are lower, but two molar proportions of water are liberated and a crystalline product results. This has a constitution similar to that of II but with the D-omhfno-tetrahydroxybutyl chain at the /3-position on the furan ring. The reaction has been applied successfully to other ketoses and... 

Glycolaldehyde also reacts in dilute solution with ethyl acetoacetate, under conditions analogous to those for D-glycerose, to give ethyl 2-methyl-3-furoate.16 The corresponding acid was identified as 2-methyl-3-furoic acid (IV). 

Hypothesis (A) is in contradiction with the experimental evidence, since glycolaldehyde andl, 3-dihydroxy-2-propanone (dihydroxyacetone)9 16 react in the same way as do the sugars. It is evident that these compounds do not possess two contiguous hydroxyl groups. Moreover, when methyl trans-0-(/3-D-glucopyranosyl)acetoacetate enol (LXIV) was treated with zinc chloride under the conditions used by West and by Garda Gonzalez, a... 

Glycolaldehyde is formed by heating 2 g. of dihydroxymaleic acid in 10 ml. of water until the evolution of carbon dioxide ceases. To the resultant solution is added 2 ml. of ethyl acetoacetate followed by 2 ml. of ethyl alcohol and 1 g. of zinc chloride. The mixture is heated for one hour on a steam bath, and the reaction mixture is extracted with benzene. The benzene extract is washed with a concentrated solution of sodium bisulfite, and evaporated, affording an oil which is saponified by heating with sodium hydroxide solution (10%) on a steam bath for one hour. It is then acidified with dilute hydrochloric acid and extracted with ether. The ethereal extract is dried with anhydrous sodium sulfate and the solvent is evaporated the residue crystallizes from ether m. p., 99°. 

D-fructose, and of their optical isomers, a truly remarkable achievement (see Fig. 1). Thus, encouragement was given to the formaldehyde theory. Paper chromatography shows formose to be a complex mixture containing glycolaldehyde, trioses, tetroses, pentoses, and hexoses.62- 63 Schmitz64 re-... 

In alkaline solution, glycolaldehyde gives rise to tetroses.160- 169 Tetroses combine with dihydroxyacetone in alkaline solution to give heptoses, as indicated by the results of paper chromatography.16 43... 

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