Fructose reactions

Thermolysis of D-fructose in acid solution provides 11 and 2-(2-hydrox-yacetyl)furan (44) as major products. Earlier work had established the presence of 44 in the product mixtures obtained after acid-catalyzed dehydrations of D-glucose and sucrose. Eleven other products were identified in the D-fructose reaction-mixture, including formic acid, acetic acid, 2-furaldehyde, levulinic acid, 2-acetyl-3-hydroxyfuran (isomaltol), and 4-hydroxy-2-(hydroxymethyl)-5-methyl-3(2//)-furanone (59). Acetic acid and formic acid can be formed by an acid-catalyzed decomposition of 2-acetyl-3-hydroxyfuran, whereas levulinic acid is a degradation prod-uct of 11. 2,3-Dihydro-3,5-dihydroxy-6-methyl-4//-pyran-4-one has also been isolated after acid treatment of D-fructose.The pyranone is a dehydration product of the pyranose form of l-deoxy-D-eo f o-2,3-hexodiulose. In aqueous acid seems to be the major reaction product of the pyranone. 

Sugars (fructose) Reaction Intermediate 4-Hydroxy-5-Methyl -3-(2H)-Furanone+ Methanal... 

D-fructose, reaction occurred in the same manner as with the sucrose synthesis and the resulting disaccharides, a-D-glucopyranosyl a-L-sorbo-furanoside89 and a-D-glucopyranosyl /3-D-xyloketofuranoside,40 were isolated. 

The dangers of consuming HFCS are apparent for at least one group of people, those who lack the enzyme needed to metabolize fructose properly. Individuals with this genetic disorder may develop serious reactions if exposed to even a very small amount of fructose, reactions that include sweating, nausea, vomiting, confusion, abdominal pain, and, in extreme cases, convulsion and coma. Fortunately, this disorder is quite rare, affecting one person in about every twenty thousand individuals. For those with the disorder, however, care must be used in the kinds of sweeteners included in the diet. 

When exposed to sunlight, it is converted to a white insoluble resin, disacryl. Oxidized by air to propenoic acid small amounts of hy-droquinone will inhibit this. Bromine forms a dibromide which is converted by barium hydroxide into DL-fructose. The acrid odour of burning fats is due to traces of propenal. It is used in the production of methionine and in controlled polymerization reactions to give acrolein polymers. ... 

Now since the configuration of carbon atoms 3, 4 and 5 of glucose and fructose art identical, it folhjws that glucosazone and fructosazone are identical in all respects. The osazone is formed however more rapidly from fructose than from glucose, and this difference in rate of formation may be used to distinguish the two sugars, provided the reactions are carried out under strictly parallel conditions (pp. 138, 338). 

Yeast contains a number of enzymes, more particularly inyertase and zymase. Invertase catalyses the hydrolysis of sucrose to glucose and fructose (cf. the catalysis of this reaction by acids, p. 369). 

Sucrose is dextro-rotatory. Fructose shows a laevo-rotation greater in magnitude than the dextro-rotation shown by glucose. Hence as the hydrolysis of sucrose proceeds, the dextro-rotation gradually falls to zero and the solution finally shows a laevo-rotation. This hydrolysis is therefore sometimes called inversion and so the enzyme which catalyses the reaction is known as " invertase. Its more systematic name is, however, sucrase. 

It is probable that many of the reactions of glucose in solution are due to the small amount of the open chain aldehyde present. If this reacts in a normal manner with a reagent, the equilibrium is disturbed, most of the cyclic form passes into (III) and ultimately the reaction proceeds to completion.-Fructose may be similarly formulated ... 

Glucose and fructose give the same osazone. This will be evident from the following schemes representing the reactions which are believed to occur ... 

Carbohydrates undergo a number of isomerization and degradation reactions under both laboratory and physiological conditions For example a mixture of glucose fructose and mannose results when any one of them is treated with aqueous base This reaction can be understood by examining the consequences of enohzation of glucose... 

There is another reaction available to the enediol intermediate Proton transfer from water to C 1 converts the enediol not to an aldose but to the ketose d fructose... 

This cleavage is a retro aldol reaction It is the reverse of the process by which d fruc tose 1 6 diphosphate would be formed by aldol addition of the enolate of dihydroxy acetone phosphate to d glyceraldehyde 3 phosphate The enzyme aldolase catalyzes both the aldol addition of the two components and m glycolysis the retro aldol cleavage of D fructose 1 6 diphosphate... 

In a similar manner, ketones can react with alcohols to form hemiketals. The analogous intramolecular reaction of a ketose sugar such as fructose yields a cyclic hemiketal (Figure 7.6). The five-membered ring thus formed is reminiscent of furan and is referred to as a furanose. The cyclic pyranose and fura-nose forms are the preferred structures for monosaccharides in aqueous solution. At equilibrium, the linear aldehyde or ketone structure is only a minor component of the mixture (generally much less than 1%). 

FIGURE 14.2 The breakdown of glucose by glycolysis provides a prime example of a metabolic pathway. Ten enzymes mediate the reactions of glycolysis. Enzyme A, fructose 1,6, hiphos-phate aldolase, catalyzes the C—C bondbreaking reaction in this pathway. 

Interestingly, in the absence of sucrose and fructose, sucrose phosphory-lase will catalyze the exchange of inorganic phosphate, P , into glucose-l-phos-phate. This reaction can be followed by using as a radioactive tracer and observing the appearance of P into glucose-l-phosphate ... 

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