CHEMISTRY & BIODIVERSITY – Vol. 9 (2012)
725
Synthesis of 2-Hydroxypropanedioic Acid (¼ Tartronic Acid; 24). Mesoxalic acid monohydrate
disodium salt (50 mg, 0.28 mmol) and NaBH4 (53 mg, 1.40 mmol) were reacted in 1.5 ml of dist. H2O.
After 2 h, the soln. was acidified with an aq. soln. of HCl. The resulting mixture was evaporated to
dryness under reduced pressure, and the dry residue was treated with a 1.5m soln. of HCl in BuOH (908
for 2 h). The residue obtained after evaporation of BuOH was purified by FC (SiO2; AcOEt).
1
Compound 24 was obtained as dibutyl ester in almost quant. yield. H-NMR (400 MHz; CD2Cl2): 0.93
(dd, J¼7.5, 7.5, 6 H); 1.37 (m, 4 H); 1.64 (m, 4 H); 4.20 (m, 4 H); 4.67 (s, CHOH). 13C-NMR (100 MHz;
CD2Cl2): 13.3; 18.9; 30.4; 66.3; 71.5; 168.7. GC/EI-MS (70 eV, rel. int.): 132 (22), 121 (9), 76 (100), 57
(90). GC/CI-MS: 250 (100, [MþNH4]þ ), 233 (40, [MþH]þ ).
Synthesis of 29. Compound 26 (32 mg, 0.35 mmol) was added to 16 (40 mg, 0.35 mmol) and NaOH
(70 mg, 1.75 mmol) in 5 ml of dist. degassed H2O. The mixture was heated at 908 for 2 d. The resulting
mixture was evaporated to dryness under reduced pressure. The acids were transformed into the
corresponding butyl esters by treatment of the dry residue with a 1.5m soln. of HCl in BuOH (908 for
2 h). The residue obtained after evaporation of BuOH was purified by FC (SiO2; CH2Cl2/cyclohexane
1
9 :1). Compound 29 was obtained as butyl ester in almost quant. yield. H-NMR (400 MHz; CD2Cl2):
0.94 (dd, J¼7.4, 7.4, 9 H); 1.38 (s, 6 H); 1.62 (s, 2 Me); 2.69 (dd, J¼16.5, 5.0, 1 H); 2.94 (dd, J¼16.5, 10.1,
1 H); 3.35 (d, J¼15.6, 1 H); 3.51 (d, J¼15.6, 1 H); 3.80 (dd, J¼10.1, 5.2, 1 H); 4.07 (m, 6 H). 13C-NMR
(100 MHz; CD2Cl2): 13.4; 19.0; 30.5; 33.3; 36.2; 41.8; 65.5; 169.6; 170.3; 170.5. GC/EI-MS: 376 (40, Mþ ),
302 (93), 274 (52), 246 (91), 230 (76), 218 (69), 200 (92), 190 (82), 175 (88), 163 (63), 156 (75), 144
(100), 131(60), 119 (45), 100 (94), 73 (39), 57 (94). HR-ESI-MS: 399.1813 ([MþNa]þ , C18H32NaO6Sþ
;
calc. 399.1817).
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