340
J Am Oil Chem Soc (2014) 91:337–348
J = 5 Hz, CHOH). 13C{1H} NMR (75 MHz, DMSO-d6,
Me4Si) d 13.90 (CH3), 22.04, 24.41, 28.42–28.97, 31.24,
33.45 (CH3(CH2)16), 62.61 (CH2OH), 65.45 (COOCH2),
69.26 (CHOH), 172.9 (CO). HRMS (ESI) m/z calculated
CH=CH2), 172.47 (CO). HRMS (ESI) m/z calculated for
C19H30NaO6 [M?Na]? = 377.19346; found: 377.19223.
Elemental analysis (found: C, 64.54; H, 8.13. C19H30O6
requires C, 64.38; H, 8.53 %).
for
C21H42NaO4
[M?Na]? = 381.29753;
found:
3-(Undec-10-enoyloxy) propan-1,2-diyl diacrylate (7):
Yellow liquid (1.8 g, 94 %). IR (ATR, neat): mmax/cm-1
2925 and 2854 (CH), 1728 (C=O), 1617 and 1636 (C=C),
381.29625. Elemental analysis (found: C, 70.14; H 12.69.
C21H42O4 requires C, 70.34; H, 11.81 %).
1
1041 and 1170 (C–O). H NMR (300 MHz, DMSO-d6,
Synthesis of the Diacrylated and Dimethacrylated
Me4Si) d 1.29 (10 H, m, CH2=CHCH2(CH2)5), 1.55 (2 H,
q, J = 5 Hz, CH2CH2CO), 2.07 (2 H, m, CH2=CHCH2),
2.34 (2 H, t, J = 7.2 Hz, CH2CO), 4.37 (4 H, m, COOCH2
and COOCH2), 5.01 (2 H, m, CH2=CHCH2), 5.38 (1 H, m,
COOCH), 5.83 (1 H, m, CH2=CHCH2), 6.01–6.41 (6 H, m,
CO–CH=CH2 and CO–CH=CH2). 13C{1H} NMR
(75 MHz, DMSO-d6, Me4Si) d 24.80, 28.71–29.12, 33.61,
33.75 (CH2=CH(CH2)8), 62.16, 62.63 (COOCH2 and
COOCH2), 69.69 (COOCH), 114.97 (CH2=CHCH2),
128.19, 128.24 (CO–CH=CH2 and CO–CH=CH2), 132.53,
132.69 (CO–CH=CH2 and CO–CH=CH2), 139.22
(CH2=CHCH2), 165.13, 165.43 (CO–CH=CH2 and CO–
CH=CH2), 172.93 (CO). HRMS (ESI) m/z calculated for
C20H30NaO6 [M?Na]? = 389.19346; found: 389.19216.
Elemental analysis (found: C, 65.27; H, 8.14. C20H30O6
requires C, 65.55; H, 8.25 %).
Monoglycerides 5–12
General Procedure
To a solution of monoglyceride (6.5 mmol) in dichloro-
methane (80 mL) was added triethylamine (15 mmol). The
solution was cooled at 0 °C under an argon atmosphere and
acryloyl or methacryloyl chloride (15 mmol) was added
dropwise. The reaction mixture was stirred 30 min at 0 °C,
then 3 h at room temperature. The solution was washed
with NaOH aqueous solution (1 mol L-1), and the organic
layer was dried over MgSO4. The solvent was evaporated
under vacuum leading to the photopolymerizable
monomer.
3-(Butyryloxy) propan-1,2-diyl diacrylate (5): Yellow
liquid (2.5 g, 91 %). IR (ATR, neat): mmax/cm-1 2920 and
2850 (CH), 1728 (C=O), 1617 and 1636 (C=C), 1167 and
3-(Stearoyloxy) propan-1,2-diyl diacrylate (8): Yellow
solid (3.5 g, 93 %), mp 32.5 °C. IR (ATR, neat): mmax
/
1
1048 (C–O). H NMR (300 MHz, DMSO-d6, Me4Si) d
cm-1 2955, 2916 and 2849 (CH), 1728 (C=O), 1617 and
1634 (C=C), 1166, 1042 (C–O). 1H NMR (300 MHz,
DMSO-d6, Me4Si) d 0.85 (3 H, t, J = 7.2 Hz, CH3), 1.24
(28 H, m, CH3(CH2)14), 1.49 (2 H, q, J = 6.9 Hz,
CH2CH2CO), 2.29 (2 H, t, J = 7.2 Hz, CH2CO), 4.30 (4 H,
m, COOCH2 and COOCH2), 5.32 (1 H, m, COOCH),
5.99–6.31 (6 H, m, CH=CH2 and CH=CH2). 13C{1H}
NMR (75 MHz, DMSO-d6, Me4Si) d 13.88 (CH3), 22.03,
24.31, 28.28–28.95, 31.24, 33.27 (CH3(CH2)16), 61.67,
62.14 (COOCH2 and COOCH2), 69.20 (COOCH), 127.72,
127.76 (CH=CH2 and CH=CH2), 132.11, 132.26 (CH=CH2
and CH=CH2), 164.66, 164.96 (CO–CH=CH2 and CO–
CH=CH2), 172.48 (CO). HRMS (ESI) m/z calculated for
C27H46NaO6 [M?Na]? = 489.31866; found: 489.31720.
Elemental analysis (found: C, 69.97; H, 10.60. C27H46O6
requires C, 69.49; H, 9.94 %).
0.89 (3 H, t, J = 7 Hz, CH3), 1.56 (2 H, m, CH2CH2CO),
2.33 (2 H, t, J = 7.2 Hz, CH2CO), 4.36 (4 H, m, COOCH2
and COOCH2), 5.38 (1 H, m, COOCH), 6.03–6.37 (6 H, m,
CH=CH2 and CH=CH2). 13C{1H} NMR (75 MHz, DMSO-
d6, Me4Si) d 13.24 (CH3), 17.79 (CH2CH2CO), 35.12
(CH2CO), 61.66, 62.14 (COOCH2 and COOCH2), 69.20
(COOCH), 127.71, 127.75 (CH=CH2 and CH=CH2),
132.09, 132.28 (CH=CH2 and CH=CH2), 164.68, 164.97
(CO–CH=CH2 and CO–CH=CH2), 172.34 (CO). HRMS
(ESI) m/z calculated for C13H18NaO6 [M?Na]?
=
293.09956; found: 293.09871. Elemental analysis (found:
C, 57.63; H, 6.46. C13H18O6 requires C, 57.77; H, 6.71 %).
3-(Decanoyloxy) propan-1,2-diyl diacrylate (6): Yellow
liquid (2.3 g, 95 %). IR (ATR, neat): mmax/cm-1 2924 and
2854 (CH), 1729 (C=O), 1617 and 1636 (C=C), 1171 and
1
1048 (C–O). H NMR (300 MHz, DMSO-d6, Me4Si) d
3-(Butyryloxy) propan-1,2-diyl bis(2-methylacrylate)
0.86 (3 H, t, J = 7 Hz, CH3), 1.23 (12 H, m, CH3(CH2)6),
1.49 (2 H, q, J = 6.8 Hz, CH2CH2CO), 2.29 (2 H, t,
J = 7.2 Hz, CH2CO), 4,26 (4 H, m, COOCH2 and
COOCH2), 5.32 (1 H, m, COOCH), 5.96–6.37 (6 H, m,
CH=CH2 and CH=CH2). 13C{1H} NMR (75 MHz, DMSO-
d6, Me4Si) d 13.86 (CH3), 22.02, 24.32, 28.29, 28.58,
28.61, 28.75, 31.21, 33.45 (CH3(CH2)8), 61.67, 62.14
(COOCH2 and COOCH2), 69.20 (COOCH), 127.71,
127.75 (CH=CH2 and CH=CH2), 132.10, 132.26 (CH=CH2
and CH=CH2), 164.65, 164.96 (CO–CH=CH2 and CO–
(9): Yellow liquid (2.3 g, 94 %). IR (ATR, neat): mmax/
cm-1 2963 (CH), 1719 (C=O), 1637 (C=C), 1145 and 1048
1
(C–O). H NMR (300 MHz, DMSO-d6, Me4Si) d 0.87 (3
H,t, J = 7 Hz, CH3), 1.54 (2 H, m, CH2CH2CO), 1.86 (6
H, S, CH3C=CH2 and CH3C=CH2), 2.28 (2 H, t,
J = 7.2 Hz, CH2CO), 4.33 (4 H, m, COOCH2 and
COOCH2), 5.31 (1 H, m, COOCH), 5.71–6.02 (4 H, m,
CH3C=CH2 and CH3C=CH2). 13C{1H} NMR (75 MHz,
DMSO-d6, Me4Si) d 13.70 (CH3), 18.21, 18.23, 18.31
(CH3CH2, CH3C=CH2 and CH3C=CH2), 35.62 (CH2CO),
123