4-Deoxytetronic acids

Additional evidence regarding the structure of DL-(3-deoxytetronic acid) was obtained (by Nef) by resolution of the acid through the brucine salt. 

Four-carbon Meta accharinic Acid DL-(3-Deoxytetronic acid), [dl-(2,4-dihydroxybutyric acid)] ... 

Dihydroxybutanoic acid, a 3-deoxytetronic acid, is the only theoretically possible four-carbon metasaccharinic acid it was isolated by Nef in the dl form (Ilab) in the course of his work on the action of sodium hydroxide on D-arabinose. It therefore constitutes the only four-carbon saccharinic acid isolated to date from a sugar-alkali reaction. Resolution of this on acid (Ilab) was accomplished by Nef, who showed that the dextrorotatory acid (Ila) upon oxidation gave rise to 2-deoxy-L-f/Z2/cero-tetraric acid [(-)-)-d-malic acid XV]. During the course of this work, several derivatives of the L and DL saccharinic acids (lib and Ilab) were prepared, but only the brucine salt of the d acid (Ila) was reported. 

The racemic 3-deoxytetronic acid (Ilab) thus produced was resolved with brucine, the more insoluble brucine salt yielding, on liberation by means of barium hydroxide, a dextrorotatory acid (Ha) which gave, on oxidation with nitric acid, a product identical with 2-deoxy-L-gd2/cero-tetraric acid [(-b)-D-malic acid XV]. Similarly, the levorotatory acid (Ilb), obtained from the mother liquor of the resolution with brucine, was oxidized with nitric acid to 2-deoxy-D-5lycero-tetraric acid [(—)-L-malic acid XIV]. The... 

Fig. 5.15 Mass spectra of the pertrimethylsilylated derivatives of (a) isovaleric acid, (b) 2-hydroxybutyric acid, (c) arabinonic acid (d) 2-deoxytetronic acid and (e) 3-deoxytetronic acid.

Unlike 2-deoxyaldonic acids the 3-deoxy analogues can lose the ester function by cleavage of the Ci-C2 bond to give M-117 (e.g. m/z 117 in lactic acid, m/z 219 in 3-deoxytetronic acid (Fig. 5.15) and related ions [e.g. m/z 231 in 3-deoxypentonic acids (M-117 90)]. 

SYNS Y-(3480 Y-BL BLO BLON BUTYRIC ACID LACTONE a-BUTYROLACTONE Y-BUTYROLACTONE (FCC) BUTYRYL LACTONE 4-DEOXYTETRONIC ACID DIHYDRO-2(3H)-FURAN-ONE FEMA No. 3291 4-HYDROXYBUTANOIC ACID LACTONE Y-HYDROXYBUTYRIC ACID CYCLIC ESTER 4-HYDROXYBUTYRIC ACID Y-LACTONE Y-... 

DEOXYRIBONUCLEOSIDE CYTOSINE see DAQ850 DEOXYRIBOSE CYTIDINE see DAQ850 DEOXYTETRARIC ACID see MANOOO 4-DEOXYTETRONIC ACID see BOVOOO P-DEOXYTHIOGUANOSINE see TFJ250 P-2 -DEOXY-6-THIOGUANOSINE MONOHYDRATE see TFJ250... 

Dihydro-2(3//) furanone 4-Hydroxy- y-lactone 4-Deoxytetronic acid... 

These 3,4-dihydroxybutanoic acids or 2-deoxytetronic acids were first prepared in the racemic form (lab) by Hanriot in 1879. The synthesis was later repeated by Nef, who studied the racemic acid in more detail and reported a few of its properties, as well as those of its phenylhydrazide and brucine salt. The constitution of the dl acid was proved by Nef by the method of synthesis, as well as by oxidation to the known 2-deoxy-DL-glycero-i it na acid (DL-malic acid). 

Synonyms BLO 1,2-Butanolide 1,4-Butanolide Butyric acid iactone a-Butyroiactone y-Butyroiactone Butyryi iactone 4-Deoxytetronic acid Dihydro-2(3H)-furanone GBL 4-Hydroxybutanoic acid iactone y-Hy-droxybutyric acid cyciic ester 4-Hydroxybutyric acid y-iactone y-Hy-droxybutyric acid iactone y-Hydroxybutyroiactone Tetrahydro-2-furanone... 

Butyric acid lactone 4-Butyrolactone a-Butyrolactone y-Butyrolactone Butyryl lactone 4-Deoxytetronic acid Dihydro-2(3H)-furanone... 

Deoxyribonucleic acid. See DNA Deoxy-Sol . See Hydrazine Deoxytetraric acid. See N-Hydroxysuccinic acid 4-Deoxytetronic acid. See Butyrolactone DEP. See Diethyl pyrocarbonate Diethyl phthalate... 

GasChromatographic/Mass Spectrometric Identification and Quantitation of Tetronic and Deoxytetronic Acids in Urine from Normal Adults and Neonates... 

Fig. 5.7 Computer plots of the mass spectra from two scans selected from the accumulated data represented in Fig. 5.6. The spectra are of the trimethylsilyl derivatives of 2-deoxytetronic acid (scan 53) and 4-hydroxyphenylacetic acid (scan 77).

Petersson (1970) also studied a number of deoxyaldonic acids. As expected, the 2-deoxy analogues do not show m z 292, in contrast to 4-deoxytetronic acids, but have a significant peak at m z 306 in pentonic and hexonic acids which is considered to arise by TMS rearrangement and include the methylene group (i.e. 292 + 14). 

Thompson, J. A., Markey, S.P. andFennessey, P.V. (1975), Gas-chromatographic mass spectrometric identification and quantitation of tetronic and deoxytetronic acids in urine from normal adults and neonates. Clin. Chem., 21,1892. 

Table 7.6 Tetronic and deoxytetronic acids (C4 polyhydroxy acids) quantified in urine from eight normal adults (from Thompson etal., 1975a).

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