1,3,2-dioxathiolane-4-methanol 2-oxide synthesis

Yield:13897-37-5 137 g

Reaction Conditions:

with thionyl chloride in dichloromethane at -5 - 15; for 24 h;Inert atmosphere;

Steps:

General procedure: A three-necked round-bottom flask (1 L) flushed withnitrogen was charged with glycerol (92 g, 1mol) and cooled down to -5 °C. Asolution of thionyl chloride (119 g, 1 mol) in CH₂Cl₂ (100mL) was added dropwise while keeping the temperature below -2 °C. A largeamount of HCl gas evolved and the reaction mixture changed from a viscouscolorless oil to a suspension and finally to a colorless solution. The mixturewas stirred for 24 hours between 10 and 15 °C. The volatiles were then removed in vacuo to yield 2 as a light yellow liquid (137 g, 96%). It was engaged in the nextstep without further purification.Compound 2:¹H NMR (400 MHz, CDCl₃):δ_H =5.08-5.03 (m, 0.5H), 4.81-4.68(m, 1.5H), 4.50 (dd,J=10Hz, J=10Hz, 0.5H), 4.35 (dd,J=10.5Hz, J=7.5HZ, 0.5H), 4.02(dd,J=16.5Hz,J=3.5Hz,0.5H),3.86-3.72 (m,1.5H),2.55 (S, 1 H) ppm; ¹³C NMR (100 MHz CDCl₃): δ_C = 83.8, 79.9, 68.3, 67.4,61.3, 60.8 ppm.

References:

Fan, Zhaoyu;Corbet, Matthieu;Zhao, Yan;De Campo, Floryan;Clacens, Jean-Marc;Pera-Titus, Marc;Métivier, Pascal;Wang, Limin [Tetrahedron Letters,2013,vol. 54,# 28,p. 3595 - 3598] Location in patent:supporting information