3
20
de Souza et al.
afforded 3-chloro-1,2-propanediol as a yellow oil containing decomposition products.
Optimal conditions and yields were obtained using 2.2 molar equivalents of water at
ꢀ
8
0 C for 3 h under reduced pressure (0.5 mm Hg).
In conclusion, a short, simple, green and an inexpensive industrially practical process
for the preparation of 3-chloro-1,2-propanediol was developed. In which the use of sol-
vents, of acidic or basic conditions is avoided. The only reagent used is water and no
waste is generated.
Experimental Section
1
H NMR spectra were determined in DMSO using a Bruker AC 400 spectrometer at operat-
ing at 400 MHz, using TMS as an internal standard. Splitting patterns are as follows: s, sin-
1
3
glet; d, duplet; m, multiplet; sl, broad signal. The C NMR spectrum was obtained using the
same apparatus described above at 100 MHz. Epichlorohydrin was purchased from Sigma-
Aldrich and was utilized as the chromatographic standard in TLC analysis. The progress of
the reactions was monitored by TLC on 2.0 cm £ 4.0 cm aluminum sheets pre-coated with
silica gel 60 (HF-254, Merck) to a thickness of 0.25 mm, eluent: hexane-ethyl acetate (1:1).
The chromatograms were visualized using a solution 10% of phosphomolybdic acid in etha-
nol. Distillation using a vacuum pump (E2M8, EDWARDS, Brazil).
Procedure
A two-phase mixture of epichlorohydrin (473.2 g, 5.11 mol) and water (110.5 g,
6
.13 mol) in a 1 L, three-necked flask immersed in an oil bath, equipped with a magnetic
ꢀ
stir bar, reflux condenser and a thermometer was stirred at 100 C for 20 h; the progress
of the reaction was monitored by TLC (hexane-ethyl acetate 1:1). After this period, an
additional amount of water was added (92.0 g, 5.11 mol) and stirring was continued at
ꢀ
1
reduced pressure (0.5 mm Hg) at 80 C to leave pure (by tlc) 3-chloro-1,2-propanediol
00 C for an additional 4 h. Excess water (47 mL) was removed by distillation under
ꢀ
(557.0 g, 99%) as a colorless oil.
3
-Chloro-1,2-propanediol, colorless oil
1
H NMR (400 MHz, DMSO-d ): d 5.10 (1H, d, CHOH, exchangeable with D O); 4.70
6
2
(1H, t, CH OH, exchangeable with D O); 3.67–3.61 (2H, m, CH Cl); 3.53–3.48 (1H, m,
CHOH); 3.43–3.34 (2H, m, CH OH). C NMR (100 MHz, DMSO-d ): d 71.1 (CHOH),
2 2 2
1
3
2
6
6
2.5 (CH OH), 47.0 (CH Cl).
2 2
References
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2
. R. Dua, S. Srivastava, S. L. Srivastava and S. K. Srivastava, Middle-East J. Sci. Res., 11, 846
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2012).
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2008).