8568
M.B. Ewonkem et al. / Tetrahedron 71 (2015) 8557e8571
3
3
2
4.39 (OeCOeCH
2.78, 31.83, 29.57, 29.52, 29.41, 29.35, 29.22, 29.10, 28.64, 25.92,
5.72, 24.99, 22.61 (CH
2
eCH
2
), 27.38 (CH
2
eCH]CHeCH
2
eCH(OH)),
CHeCH
CHeCH
2
eCH(O)),
eCH(OH)),
125.23(CH]CHeCH
66.42 (CH eCH
Cl), 40.94 (CH
eCH(OH)), 35.38
34.38 (OeCOeCH
2
eCH(O)),
eOeCOeCH
eCH eOeCOeCH
(CH]CHeCH eCH(OH)e
), 27.39 (CH eCH]
71.53(CH]
), 64.41
Cl), 36.87
2
2
2
2
2
), 14.07 (CH
3
eCH
2
). MS (ESI) positive mode
(CH
(CH]CHeCH
CH eCH ),
CHeCH
28.45, 25.93, 25.74, 24.99, 22.62 (CH
2
eCH
2
eOeCOeCH
2
2
2
2
þ
þ
(m/z): calcd for C30
H
58
O
4
, [MþH] 483.4398, found [MþH]
2
2
4
83.4376.
2
2
2
eCH
2
2
2
eCH(OH), 31.84, 29.51, 29.36, 29.25, 29.14, 29.11, 28.66,
), 14.08 (CH eCH ). MS (ESI)
Cl, [MþNa] 582.4019;
4.3.1.2. Monoester 3c (n¼2). The monoester 3c was prepared by
2
3
2
þ
chemoenzymatic transesterification of 1.25 mmol of ethylene gly-
col 2c and 2.5 mmol of Methyl ricinoleate 1 (R¼H) in tert-BuOH in
the presence of C. antarctica lipase at room temperature for 24 h.
The reaction mixture was dissolved in diethyl ether, the lipase was
filtered off and the solvent was removed under reduced pressure.
The mixture of esters was purified by silica gel flash column
chromatography with of petroleum ether/diethyl ether: 7/1, 6/4
then 1/1 (v/v) and 0.35 g (40%) of monoester 3c was obtained.
positive mode (m/z): calcd for C32
59 5
H O
found [MþH]þ 582.4076.
4.3.2.2. Dichloroacetate 1,12-dodecanemonoricinoleate 9a. 1.51 g
ꢁ1
(79%). FTIR (NaCl)
(COCH Cl), 1737 (carbonylic ester), 1473, 1311, 1291 (CH
1181,1020,869, 798(CeCl). HNMR(CDCl
m, CH eCH]CHeCH eCH(O)), 5.33 (1H, m, CH
CHeCH eCH(O)), 4.98(1H, m, CH]CHeCH eCH(O)eCO), 4.21(2H, t,
J ¼6.5 Hz, CH eCH eOeCOeCH Cl), 4.07, 4.03 (2H, 2d, Jgem¼14.5 Hz,
CHeOeCOeCH Cl), 4.08 (2H, s, CH eCH eOeCOeCH Cl), 4.07 (2H, t,
J ¼7.0 Hz, CH eCH eOeCOeCH ), 2.37 (2H, m, CH]
CHeCH eCH ), 2.04 (2H,
eCH(O)), 2.31 (2H, t, J ¼7.5 Hz, OeCOeCH
q, J ¼6.5 Hz, CH eCH]CHeCH eCH(O)), 1.62, 1.31 (40H, m, CH ),
ppm
Cl), 167.02
eCH(O)), 123.66
eCH(O)), 66.41 (CH]CHeCH eCH(O)eCO),
eOeCOeCH ), 64.40 (CH eCH eOeCOeCH Cl),
41.12 (CHeOeCOeCH Cl), 40.93 (CH eCH eOeCOeCH Cl), 34.37
(CH]CHeCH eCH(O)), 33.48 (OeCOeCH eCH ), 27.33 (CH eCH]
CHeCH eCH(O)), 31.82, 31.68, 29.50, 29.24, 29.17, 29.11, 28.66, 28.44,
25.92, 25.75, 25.23, 24.99, 22.55 (CH
n
max (cm ) 3014 (CH]CH), 2929, 2853, 1764
Cl), 1259,
ppm 5.51(1H,
eCH]
2
2
1
3
, 500MHz)d
2
2
2
ꢁ
1
FTIR
carbonylic ester),1455,1388,1255, 1081,1040, 876. H NMR (CDCl
00 MHz) ppm 5.55 (1H, m, CH eCH]CHeCH eCH(OH)), 5.40
1H, m, CH eCH]CHeCH
eCH(OH)), 4.21 (2H, t, J ¼4.5 Hz,
CH eCH
eOeCO), 3.82 (2H, t, J ¼4.5 Hz, CH
CH]CHeCH
.20 (2H, t, J ¼7.0 Hz, CH]CHeCH
n
max (cm ) 3396 (OH), 3007 (CH]CH), 2927, 2855, 1737
2
2
1
3
(
5
(
3
,
2
2
2
d
2
2
2
2
2
2
3
3
2
2
2
2
2
3
3
2
2
2
eOH), 3.61 (1H, m,
eCH(OH)), 2.34 (2H, t, J ¼7.5 Hz, OeCOeCH eCH ),
eCH(OH)), 2.04 (2H, q,
eCH(OH)), 1.62, 1.45, 1.30 (20H, m,
2
2
2
3
3
2
2
2
2
2
2
3
3
13
2
2
0.90 (3H, t, J ¼7.0 Hz, CH
173.95 (COeCH eCH ), 167.39 (CH
(CHeOeCOeCH Cl), 133.11 (CH eCH]CHeCH
(CH eCH]CHeCH
66.41 (CH eCH
3
eCH
2
). C NMR (CDCl
3
, 125 MHz) d
3
J ¼7.0 Hz, CH
CH
), 0.88 (3H, t, J ¼7.0 Hz, CH
ppm 174.22 (CO), 133.41 (CH
CH eCH]CHeCH eCH(OH)), 71.50 (CH]CHeCH
5.92 (CH eOH), 61.31 (CH eCH eOeCO), 36.83 (CH]
eCH ), 35.34 (CH]CHeCH eCH(OH)), 34.16
), 27.34 (CH eCH]CHeCH eCH(OH)), 31.84,
0.95, 29.70, 29.53, 29.35, 29.03, 25.72, 24.86, 22.62 (CH ), 14.10
2
eCH]CHeCH
2
2
2
2
eCH eOeCOeCH
2
2
3
13
2
3
eCH
2
). C NMR (CDCl
eCH(OH)), 125.22
eCH(OH)),
3
, 125 MHz)
2
2
2
d
2
eCH]CHeCH
2
2
2
2
(
6
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
CHeCH(OH)eCH
2
2
2
2
2
2
2
(
OeCOeCH
2
eCH
2
2
2
2
3
2
2
), 14.04 (CH
3
2
eCH ). MS (ESI)
þ
(
[
CH
3
eCH
2
). MS (ESI) positive mode (m/z): calcd for C20
H
38
O
4
,
positive mode (m/z):calcd for C34
60 6 2
H O Cl , [MþNa] 657.3694, found
MþNa] 365.3945., found [MþNa]þ 365.4003.
þ
[MþNa]þ 657.3568.
4
.3.2. Chloroacetates monoesters of ricinoleic acid 8a (n¼12) and 9a
4.3.2.3. Dichloroacetate 1,10-decanemonoricinoleate 9b. 1.28 g
ꢁ
1
(
n¼12), 9b (n¼10) and 9c (n¼2). The monochloroacetate in-
termediate 8a was obtained by magnetic stirring of monoester 3d
1.7 g, 3.5 mmol) and an excess (8 mol excess) of chloroacetyl
(78%). FTIR (NaCl)
(COCH Cl), 1736 (carbonylic ester), 1472, 1286 (CH
1009, 787 (CeCl). H NMR (CDCl
CH eCH]CHeCH eCH(O)), 5.31
CHeCH eCH(O)), 4.96 (1H, m, CH]CHeCH
J ¼7.0 Hz, CH eCH eOeCOeCH Cl), 4.06, 4.01 (2H, 2d, Jgem¼14.5 Hz,
CHeOeCOeCH Cl), 4.06 (2H, s, CH eCH eOeCOeCH Cl), 4.05 (2H, t,
J ¼7.0 Hz, CH eCH eOeCOeCH ), 2.31 (4H, 2t, J ¼7.5 Hz,
OeCOeCH eCH CH]CHeCH
eCH(O)), 2.02 (2H, q, J ¼7.0 Hz,
CH eCH]CHeCH eCH(O)), 1.63, 1.30 (36H, m, CH ), 0.88 (3H, t,
J ¼7.0 Hz, CH eCH ppm 173.91
(COeCH eCH ), 166.97 CH eCH]
eCH(O), 123.60 (CH eCH(O)), 66.33 (CH]
eCH(O)eCO), 66.33 (CH eOeCOeCH ), 64.32
Cl), 41.07 (CHeOeCOeCH Cl), 40.88
Cl), 34.31 (CH]CHeCH eCH(O)), 33.42
eCH]CHeCH eCH(O)), 31.75, 31.62,
9.42, 29.32, 29.06, 28.58, 25.84, 25.68, 25.17, 24.93, 22.50 (CH ),
13.99 (CH eCH ). MS (ESI) positive mode (m/z): calcd for
Cl
, [MþNa] 629.5745, found [MþNa] 629.5694.
n
max (cm ) 3011 (CH]CH), 2928, 2856, 1760
Cl), 1257, 1175,
ppm 5.49 (1H, m,
m, CH eCH]
eCH(O)eCO), 4.19 (2H, t,
2
2
1
(
3
, 500 MHz)
(1H,
d
chloride 5 (2.80 ml, 35 mmol) in dry diethyl ether at room tem-
perature for 1 h. TLC monitored the reaction. The reaction mixture
2
2
2
2
2
3
was washed with a solution of 5% NaHCO
pH 5.4. The organic phase was separated, dried over anhydrous
MgSO , filtered and the solvent was removed under reduced
pressure. The residue was purified by silica gel flash column chro-
matography using 1,2-dichloroethane as eluent to give 1.3 g (66%)
of pure intermediate compound 8a.
For the asymmetric dichloroacetate intermediates 9, the syn-
thesis procedure was similar to the procedure used for the syn-
thesis of symmetric dichloroacetate compounds 6 using Monoester
3
and distilled water until
2
2
2
2
2
2
2
3
3
4
2
2
2
3
2
2
2
2
2
2
3
13
3
2
). C NMR (CDCl
(COeCH eCl), 133.05
eCH]CHeCH
eCH
3
, 125 MHz) d
2
2
2
2
CHeCH
CHeCH
2
2
2
2
2
2
2
3
a (1.23 g, 27 mmol) for the synthesis of the intermediate 9a,
(CH
(CH
(OeCOeCH
2
eCH
eCH
2
eOeCOeCH
eOeCOeCH
eCH
2
2
Monoester 3d (1.45 g, 32 mmol) for the synthesis of 9b and
Monoester 3c (0.35 g, 10.2 mmol) for the synthesis of 9c.
2
2
2
2
2
2
), 28.38 (CH
2
2
2
2
4
.3.2.1. Monochloroacetate 1,12-dodecanemonoricinoleate 8a
3
2
ꢁ1
þ
þ
(
1
n¼12). FTIR
n
max (cm ) 3285 (OH), 3026 (CH]CH), 2930, 2849,
C
H O
32 56 6
2
759 (COCH Cl), 1735 (carbonylic ester), 1471, 1454, 1311, 1284
2
(
CH
2
Cl), 1247, 1189, 1023, 869, 793 (CeCl).
4.3.2.4. Dichloroacetate 1,2-ethanemonoricinoleate 9c. 0.37
g
1
ꢁ1
H NMR (CDCl
3
, 500 MHz)
d
ppm 5.57 (1H, m, CH
eCH]CHeCH eCH(OH)), 4.20
eOeCOeCH Cl), 4.07 (2H, s,
4.06 (2H,
), 3.63 (1H, m, CH]CHeCH
2
eCH]
(73%). FTIR (NaCl)
1759 (COCH
1291 (CH Cl), 1254, 1172, 1037, 964, 863, 778 (CeCl). H NMR
(CDCl ,500 MHz) ppm 5.48 (1H, m, CH eCH]CHeCH eCH(O)),
5.31 (1H, m, CH eCH]CHeCH eCH(O)), 4.95 (1H, m, CH]
CHeCH 4.40
CH eCH Cl), 4.04, 4.01 (2H, 2d,
eCH eOeCOeCH
eOeCOeCH
), 2.33 (4H, 2t, J ¼7.5 Hz,
, CH]CHeCH
eCH(O)), 2.02 (2H, q, J ¼7.0 Hz,
n
max (cm ) 3014 (CH]CH), 2962, 2927, 2856,
CHeCH eCH(OH)), 5.41 (1H, m, CH
2
2
2
2
Cl), 1740 (carbonylic ester), 1468, 1416, 1384, 1309,
3
1
(
CH
CH
2H, t, J ¼7.0 Hz, CH
2
eCH
2
2
2
3
2
eCH
eCH
2
eOeCOeCH
eOeCOeCH
2
Cl),
t,
J ¼7.0
Hz,
3
d
2
2
2
2
2
2
eCH(OH)), 2.30
2
2
3
3
3
(
2H, t, J ¼7.5 Hz, OeCOeCH
CHeCH
eCH(OH)), 2.06 (2H, q, J ¼7.0 Hz, CH
CHeCH eCH(OH)), 1.66, 1.48, 1.30 (40H, m, CH ), 0.90 (3H, t,
ppm 174.00
eCl), 133.40 (CH eCH]
2
eCH
2
), 2.22 (2H, t, J ¼6.5 Hz, CH]
2
eCH(O)eCO),
(2H,
2t,
J ¼4.5
gem¼14.5 Hz,
Cl), 4.31 (2H,
Hz,
3
2
2
eCH]
2
2
eOeCOeCH
2
J
2
2
CHeOeCOeCH
2
Cl), 4.09 (2H, s, CH
2t, J ¼7.5 Hz, CH eCH
OeCOeCH eCH
2
2
2
3
13
3
3
J ¼7.0 Hz, CH
COeCH eCH
3
eCH
2
). C NMR (CDCl
3
, 125 MHz)
d
2
2
2
3
(
2
2
), 167.41 (COeCH
2
2
2
2
2