Organic Process Research & Development
Article
for 10 h in the same temperature range. Upon completion of
the reaction (as determined by TLC), 36% (w/w) hydrochloric
acid (19 kg, 187 mol) was slowly charged to the stirred mixture
whilst maintaining the temperature in the range of −5 to 0 °C.
The resulting mixture was stirred for 1 h at same temperature
before being filtered. The filter cake was then washed with
tetrahydrofuran (3 × 5 L), and the combined filtrate and
washings were concentrated under vacuum to give the crude
product as a viscous liquid containing a small quantity of white
solid. The crude product was then placed in a 200 L glass-lined
reactor (A), followed by methanol (80 L). Methanol (48 L),
water (30 L), and NaOH (2 kg, 50 mol) were then added
sequentially to a separate reactor (B). Both reactors were
heated to 85 °C, and the azeotropic mixture of methanol and
trimethyl borate that was generated in reactor A was transferred
to reactor B, where the trimethyl borate was hydrolyzed to give
methanol, which was evaporated and condensed back into
reactor A. The reaction was monitored by combustion until the
green flame of trimethyl borate disappeared (ca. 10 h), at which
point the solution in reactor A was sequentially concentrated
and distilled (181−184 °C/20 mmHg) to give (S)-1,2,4-
(6) Schlesinger, H. I.; Brown, H. C.; Mayfield, D. L.; Gilbreath, J. R. J.
Am. Chem. Soc. 1953, 75 (1), 213−215.
butanetriol (12.6 kg, 76% yield for two steps) as a light-yellow
1
oil. H NMR (D O): δ 1.57 (1H, m), 1.66 (1H, m), 3.40 (1H,
2
13
m), 3.51 (1H, m), 3.63 (2H, m), 3.73 (1H, m). C NMR
D O): δ 34.74, 58.29, 65.54, 68.85. [α] = −25.2 (c = 1,
2
0
(
2
D
3a
20
MeOH) (lit [α]D = −25.5°).
AUTHOR INFORMATION
5643811.
5643811.
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*
6
*
6
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The authors thank Dr. Fr-Chen for his continued support of
this research project.
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dx.doi.org/10.1021/op400271k | Org. Process Res. Dev. XXXX, XXX, XXX−XXX