1
144
J Am Oil Chem Soc (2011) 88:1143–1151
(
09), and that the method was not suitable for fats and oils
J = 5.2 Hz, 1H), 3.62 (dd, J = 5.82, 11.3 Hz, 1H), 2.65 (bs,
1H), 2.35 (t, J = 7.5 Hz, 2H), 1.63 (quint, J = 7.4 Hz, 2H),
which include glycidyl esters.
1
.26 (m, 24H), 0.88 (t, J = 6.8 Hz, 3H); C NMR
3
1
(
75 MHz, CDCl ) d 173.1, 68.8, 68.4, 47.8, 33.9, 31.9,
3
Experimental Procedures
29.6–29.1 (10 9 CH ), 25.1, 22.8, 14.1; MS (ESI)
2
?
m/z 371.4 [M ? Na] ; Anal. Calcd for C H O Cl: C,
65.40; H, 10.69. Found: C, 65.44; H, 10.52.
1
9 37 3
Materials
3
-MCPD, 3-MCPD-d , glycidol, phenylboronic acid,
5
Procedure B
sodium methoxide/methanol solution, starting materials for
syntheses, and solvents were purchased from Wako Pure
Chemical Industries, Ltd. (Osaka, Japan). NaCl and acetic
acid were purchased from Nakalai Tesque Co. Ltd. (Kyoto,
Japan). Soybean oil was the product of Ueda Oils and Fats
Palmitic acid (1.0 g, 3.90 mmol) was dissolved in dry
methylene chloride (20 mL) at 0 °C under argon
atmosphere. 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide
hydrochloride (EDCÁHCl) (0.75 g, 3.90 mmol), N,N-diiso-
propylethylamine (DIEA) (0.50 g, 3.90 mmol), and N,N-
dimethylaminopyridine (DMAP) (0.048 g, 0.39 mmol)
were added to the solution. The reaction mixture was stirred
for 5 min, and then cooled down. Glycidol (0.26 mL,
MFG Co. Ltd. (Kobe, Japan). D O (99.96 atom% D) and
2
CDCl3 (99.8 atom% D) were purchased from Aldrich
Chemical Company, Inc. (Milwaukee, WI, USA). Other
chemicals were of the analytical grade.
3
1
.90 mmol) was added to the mixture, and stirred for
0 min, then allowed to warm up to room temperature.
Synthesis of Glycidyl Esters
Glycidyl Palmitate
After the reaction was complete, the methylene chloride
solution was washed with water (20 mL), 0.1 M hydrogen
chloride solution (20 mL), sat. sodium hydrogen carbonate
solution (20 mL), and finally brine (20 mL). The solvent
was evaporated to dryness, and the residue was purified by
silica gel column chromatography (ethyl acetate/hexane =
1/1, vol/vol) to give glycidyl palmitate (0.96 g, 79%) as a
white solid.
Procedure A
Glycidol (0.27 g, 3.64 mmol) was dissolved in dry pyridine
(
20 mL) at 0 °C in a three-necked flask equipped with a
drying tube. Palmitoyl chloride (1.0 g, 3.64 mmol) was
added to the solution in four portions at intervals of
3-Chloro-2-Hydroxypropyl Palmitate
(3-MCPD Palmitate)
1
0 min. The reaction mixture was stirred overnight at room
temperature, and the solvent was removed by evaporation.
The residue was extracted with chloroform (20 mL), and
washed with water (20 mL), 0.1 M hydrogen chloride
solution (20 mL), sat. sodium hydrogen carbonate solution
3-Chloro-2-hydroxy propanol (0.40 g, 3.64 mmol) was
dissolved in dry pyridine (20 mL) at 0 °C in a three-necked
flask equipped with a drying tube. Palmitoyl chloride
(1.0 g, 3.64 mmol) was added to the solution in four por-
tions at intervals of 10 min. The reaction mixture was
stirred for 2 h at room temperature. The solvent was then
removed by evaporation. The residue was extracted with
chloroform (20 mL), washed with water (20 mL), 0.1 M
hydrogen chloride solution (20 mL), sat. sodium hydrogen
carbonate solution (20 mL), and finally brine (20 mL). The
solvent was evaporated to dryness. The residue was puri-
fied by flash chromatography on silica gel (ethyl acetate/
hexane = 1/2, vol/vol) to give 3-chloro-2-hydroxypropyl
palmitate (0.82 g, 64%) as a white solid, 3-chloropropyl
1,2-dipalmitate (0.040 g, 2%) as a white solid, and
3-chloro-1-hydroxypropyl palmitate (0.062 g, 5%) as a
white solid. 3-Chloropropyl 1,2-dipalmitate: IR (neat)
(
20 mL), and finally brine (20 mL). The solvent was
evaporated to dryness. The residue was purified by flash
chromatography on silica gel (ethyl acetate/hexane = 1/1,
vol/vol) to give glycidyl palmitate (0.80 g, 70%) as a white
solid and 3-chloro-2-hydroxypropyl palmitate (0.12 g, 9%)
as a white solid. Glycidyl palmitate: IR (neat) 2,912, 2,844,
1
1
4
1
2
1
,737, 1,471, 1,456, 846; H NMR (300 MHz, CDCl ) d
3
.40 (dd, J = 3.1, 12.2 Hz, 1H), 3.91 (dd, J = 6.3, 12.2 Hz,
H), 3.26 (m, 1H), 2.84 (t, J = 4.6 Hz, 1H), 2.65 (dd, J =
.6, 4.8 Hz, 1H), 2.35 (t, J = 7.6 Hz, 2H), 1.63 (m, 2H),
1
3
.26 (m, 24H), 0.88 (t, J = 6.5 Hz, 3H); C NMR
(
75 MHz, CDCl3) d 173.5, 64.7, 49.3, 44.6, 30.0, 31.9,
9.6–29.1 (10 9 CH ), 24.8, 22.6, 14.0; MS (ESI)
2
2
?
m/z 335.4 [M ? Na] ; Anal. Calcd for C H O : C, 73.03;
H, 11.61. Found: C, 73.06; H, 11.51. 3-Chloro-2-
1
9 36 3
1
2,913, 2,844, 1,728, 1,471, 1,253; H NMR (300 MHz,
hydroxypropyl palmitate (3-MCPD palmitate): IR (neat)
1
,436, 2,931, 1,737, 1,465, 1,180, 719; H NMR
CDCl ) d 5.22 (m, 1H), 4.28 (dd, J = 4.4, 11.8 Hz, 2H),
3
3
3.66 (dd, J = 5.4, 11.8 Hz, 2H), 2.33 (m, 4H), 1.63 (m, 4H),
1
1.26 (m, 48H), 0.88 (t, J = 6.8 Hz, 6H); C NMR
3
(
300 MHz, CDCl ) d 4.22 (d, J = 5.2 Hz, 2H), 3.91 (quint,
3
1
23