230
M. Tryznowski et al. / Polymer 80 (2015) 228e236
dryness and crystallized from ethyl acetate. A total of 876 g
(4.01 mol) of 2 was obtained as a white solid with 79% yield (with
further purification.
NIPU 1; Yield 99.5%; 1H NMR (DMSO-d6, 400 MHz);
respect to
a
,
a
-diglycerol).
d
(ppm) ¼ 7.08 (bs, 1.82H, NH(E)), 6.76 (bs, 0.18H, NH(Z)), 4.98 (bs,
Yield 876 g (79%); mp 66e67 ꢀC (lit [52]. 62e64 ꢀC); density
1.4H, OH), 4.79 (bs, 0.6H, OH), 4.68 (bs, 0.8H, CHO(CO)N), 3.98e3.78
(m, 2.5H, CH2OCH2), 3.78e3.66 (m, 1.4H, CHOH), 3.56e3.21 (m,
5.3H, CH2O), 3.00 (bs, 4H, CH2NH); 13C NMR (DMSO-d6, 100 MHz);
1.4981
0.022 g/mL. 1H NMR (DMSO-d6, 400 MHz);
d
(ppm) ¼ 4.98e4.89 (m, 2H, CH2CHCH2), 4.52 (t, 2H, J ¼ 8.5 Hz,
OCH2 cycl.), 4,28e4.20 (m, 2H, OCH2 cycl.), 3.79e3.72 (m, 2H, OCH2),
d
(ppm) ¼ 156.4, 156.0 (C]O), 73.3, 72.6, 72.5, 69.9, 69.8, 67.8, 65.6,
3.71e3.64 (m, 2H, OCH2)); 13C NMR (DMSO-d6, 100 MHz);
60.1 (CH2O and CHO), 40.2 (CH2NH); FTIR (KBr):
2944, 2878, 1786, 1697, 1533, 1262, 1140, 776.
n
(cmꢁ1) ¼ 3337,
d
(ppm) ¼ 154.8 (C]O), 75.4 (CH), 70.4 (CH2 cycl.), 65.9 (CH2); FTIR
(KBr):
n
(cmꢁ1) ¼ 2994, 2927, 2886, 1785, 1486, 1372, 1343, 1252,
NIPU 2; Yield 99%; 1H NMR (DMSO-d6, 400 MHz);
d
(ppm) ¼ 7.11
1177, 1148, 1113, 1057, 959, 855, 770, 714, 598.
(bs, 1.82H, NH(E)), 6.75 (bs, 0.18H, NH(Z)), 4.91 (bs, 1.3H, OH), 4.76
(bs, 0.7H, OH), 4.62 (bs, 0.8H, CHO(CO)N), 3.95e3.77 (m, 2.5H,
CH2OCH2), 3.77e3.66 (m, 1.4H, CHOH), 3.60e3.20 (m, 5.3H, CH2O),
2.93 (bs, 4H, CH2NH), 1.34 (bs, 4H, CH2); 13C NMR (DMSO-d6,
Crystal data for
2
(enantiomers): orthorombic,
P
b c a,
b
a ¼ 7.6790(8) Å, b ¼ 11.7916(12) Å, c ¼ 20.679(2) Å,
a
¼ 90ꢀ,
¼ 90ꢀ,
g
¼ 90ꢀ, V ¼ 1872.4(3) Å3 Z ¼ 8,
m
¼ 1.219 mmꢁ1, Dcalc ¼ 1.548 g/cm3,
13 108 reflection measured (4.28 ꢂ 2
Q
ꢂ 70.05ꢀ), 1783 independent
100 MHz);
d
(ppm) ¼ 156.3, 156.0 (C]O), 73.3, 72.7, 72.6, 70.0, 67.9,
(R(int) ¼ 0.0444). The final R1 was 0.0396 (I > 2
s
(I)) and wR2 was
65.5, 60.1 (CH2O and CHO), 40.0 (CH2NH), 29.6 (CH2); FTIR (KBr): n
0.1065 (all data).
(cmꢁ1) ¼ 3341, 2932, 2869, 1786, 1698, 1534, 1452, 1254, 1136, 775.
NIPU 3; Yield 98%; 1H NMR (DMSO-d6, 400 MHz);
2.3.2. Hydrolysis of five-membered bis(cyclic carbonate)
d
(ppm) ¼ 7.09 (bs, 1.83H, NH(E)), 6.73 (bs, 0.17H, NH(Z)), 4.95 (bs,
(1a) In a 100 mL round bottom flask equipped with a magnetic
stirrer and a reflux condenser, 10 g (45.9 mmol) of bis(cyclic car-
bonate) 2 was placed followed by 50 mL of methanol, 50 mL of
water and 2 g (14.5 mmol) of potassium carbonate. The resulting
mixture was stirred at reflux for 2 h. The mixture was evaporated to
dryness. The residue was dissolved in methanol. The solid salt was
filtrated off and the solution evaporated to dryness yielding 7.54 g
(99%) of tetrol 1a as a light viscous oil.
1.5H, OH), 4.77 (bs, 0.5H, OH), 4.66 (bs, 0.7H, CHO(CO)N), 3.96e3.78
(m, 2.7H, CH2OCH2), 3.78e3.67 (m, 1.5H, CHOH), 3.55e3.25 (m,
5.1H, CH2O), 2.97e2.86 (m, 4H, CH2NH); 1.35 (bs, 4H, CH2), 1.20 (bs,
4H, CH2); 13C NMR (DMSO-d6, 100 MHz);
d
(ppm) ¼ 156.4, 156.0
(C]O), 73.1, 73.0, 72.7, 72.6, 70.5, 70.0, 69.8, 67.9, 65.5, 63.0, 60.2
(CH2O and CHO), 40.3 (CH2NH), 29.5, 26.1 (CH2); FTIR (KBr):
n
(cmꢁ1) ¼ 3338, 2933, 2861, 1786, 1699, 1538, 1458, 1258, 1137, 777.
NIPU 4; Yield 98%; 1H NMR (DMSO-d6, 400 MHz);
d
(ppm) ¼ 7.10
Yield 7.54 g (99%); density 1.2961
(DMSO-d6, 400 MHz);
(ppm) ¼ 4.65 (d, 2H, J ¼ 4.8 Hz, OH), 4.51 (t,
2H, J ¼ 5.8 Hz, OH), 3.60e3.49 (m, 2H, CH2CHCH2), 3.45e3.22 (m,
0.022 g/mL.; 1H NMR
(bs, 1.82H, NH(E)), 6.75 (bs, 0.18H, NH(Z)), 4.92 (bs, 1.6H, OH), 4.75
(bs, 0.4H, OH), 4.61 (bs, 0.8H, CHO(CO)N), 3.97e3.76 (m, 2.7H,
CH2OCH2), 3.78e3.67 (m, 1.5H, CHOH), 3.58e3.23 (m, 5.0H, CH2O),
d
8H, OCH2); 13C NMR (DMSO-d6, 100 MHz);
d
(ppm) ¼ 72.9 (OCH2),
2.97e2.86 (m, 4H, CH2NH); 1.35 (bs, 4H, CH2), 1.20 (bs, 8H, CH2); 13
C
70.5 (CH), 63.1 (CH2OH); FTIR (KBr):
1659, 1130, 1042, 931, 867.
n
(cmꢁ1) ¼ 3364, 2922, 2880,
NMR (DMSO-d6, 100 MHz);
72.9, 72.7, 72.6, 70.5, 70.4, 69.9, 67.8, 66.0, 65.5, 60.1 (CH2O and
d
(ppm) ¼ 156.3, 155.9 (C]O), 73.0,
CHO), 40.8 (CH2NH), 29.3, 28.8, 26.5 (CH2); FTIR (KBr):
n
2.3.3. Synthesis of model adduct of bis(cyclic carbonate) 2 with
butylamine, (3)
(cmꢁ1) ¼ 3335, 2927, 2857, 1786, 1699, 1533, 1464, 1255, 1136, 779.
NIPU 5; Yield 98%1H NMR (DMSO-d6, 400 MHz);
d
(ppm) ¼ 7.08
21.8 g (0.1 mol) of bis(cyclic carbonate) was placed in a 250 mL
round bottom flask equipped with a mechanical stirrer and a ni-
trogen inlet. The solid was melted under nitrogen atmosphere at
70 ꢀC. Then 36.6 g (0.5 mol) of n-butylamine was added in portions
during 30 min. The reaction mixture was stirred at 80 ꢀC for 8 h. The
reaction mixture was cooled down, the excess amine was evapo-
rated and the product was crystalized from diethyl ether.
Yield 31.4 g (86%); mp 107e108 ꢀC; 1H NMR (DMSO-d6,
(bs, 1.85H, NH(E)), 6.73 (bs, 0.15H, NH(Z)), 4.92 (bs, 1.55H, OH), 4.74
(bs, 0.45H, OH), 4.65 (bs, 0.6H, CHO(CO)N), 3.94e3.77 (m, 2.9H,
CH2OCH2), 3.77e3.65 (m, 1.5H, CHOH), 3.54e3.23 (m, 5.0H, CH2O),
2.99e2.86 (m, 4H, CH2NH); 1.35 (bs, 4H, CH2), 1.22(bs, 12H, CH2);
13C NMR (DMSO-d6, 100 MHz);
72.7, 72.5, 70.2, 70.4, 69.9, 67.8, 66.3, 60.1 (CH2O and CHO), 40.3
(CH2NH), 29.5, 29.1, 28.8, 26.3 (CH2); FTIR (KBr):
2921, 2851, 1788, 1697, 1538, 1468, 1245, 1143, 778.
NIPU 6; Yield 96%; 1H NMR (DMSO-d6, 400 MHz);
d
(ppm) ¼ 156.3, 155.9 (C]O), 73.1,
n
(cmꢁ1) ¼ 3335,
400 MHz);
d
(ppm) ¼ 7.11 (t, NH(E), 1.8H, J ¼ 5.7 Hz), 6.7 (bs, 0.2H,
d
(ppm) ¼ 7.12
NH(Z)), 4.92 (d, 2H, OH, 5.1 Hz), 3.92 (dd, 2H, CH2O(CO), J1¼11.0 Hz,
J2¼4.7 Hz), 3.84 (dd, 2H, CH2O(CO), J1¼11.0 Hz, J2¼6.2 Hz),
3.78e3.68 (m, 2H, CH), 3.41e3.30 (m, 4H, CH2OCH2), 2.95 (q, 2H,
CH2NH, J ¼ 6.7 Hz), 1.41e1.20 (m, 8H, CH2), 0.85 (t, 6H, CH3,
(bs,1.81H, NH(E)), 6.76 (bs, 0.19H, NH(Z)), 4.94 (bs, 1.3H, OH), 4.74(bs,
0.7H, OH), 4.65 (bs, 0.7H, CHO(CO)N), 3.99e3.79 (m, 2.6H, CH2O),
3.79e3.65 (m, 1.5H, CHOH), 3.56e3.21 (m, 13.2H, CH2O), 3.16e3.04
(m, 4H, CH2NH); 13C NMR (DMSO-d6, 100 MHz);
d
(ppm) ¼ 156.3,
J ¼ 7.3 Hz); 13C NMR (DMSO-d6, 100 MHz);
d
(ppm) ¼ 156.3 (C]O),
156.0 (C]O), 73.3, 72.6, 72.5, 69.9, 69.8, 69.5, 69.1, 67.7, 65.5, 60.1
72.7 (CH2OCH2), 67.9 (CH), 65.5 (CH2O(CO)), 40.0 (CH2NH), 31.6
(CH2O and CHO), 40.1 (CH2NH); FTIR (KBr):
n
(cmꢁ1) ¼ 3339, 2938,
(CH2), 19.5 (CH2), 13.8(CH3); FTIR (KBr):
1690, 1673, 1555, 1283, 1260.
n
(cmꢁ1) ¼ 3320, 2958,
2875, 1787, 1699, 1533, 1458, 1257, 1121, 1049, 776.
NIPU 7; Yield 97%; 1H NMR (DMSO-d6, 400 MHz);
d
(ppm) ¼ 7.10
(bs, 1.83H, NH(E)), 6.75 (bs, 0.17H, NH(Z)), 4.88 (bs, 2H, OH), 4.65 (bs,
0.7H, CHO(CO)N), 3.97e3.78 (m, 2.7H, CH2O), 3.78e3.66 (m, 1.6H,
CHOH), 3.57e3.23 (m, 17H, CH2O), 3.16e3.04 (m, 4H, CH2NH),
1.65e1.54 (m, 4H, CH2); 13C NMR (DMSO-d6, 100 MHz);
2.3.4. General procedure for the preparation of non-isocyanate
polyurethanes (NIPUs)
NIPUs were synthesized by the reaction of five-membered
bis(cyclic carbonate) 2 with various diamines. 54.5 g (0.25 mol) of
bis(cyclic carbonate) was placed in a 250 mL round bottom flask
equipped with a mechanical stirrer and a nitrogen inlet. The solid
was melted under nitrogen atmosphere at 80 ꢀC. Then 0.25 mol of
an appropriate diamine (see Table 1) was added in portions during
30 min and the temperature increased up to 150 ꢀC. The reaction
mixture was stirred at this temperature for 8 h. Then the reaction
mixture was cooled down and the polymers analyzed without
d
(ppm) ¼ 156.1, 155.8 (C]O), 73.0, 72.9, 72.6, 72.4, 70.4, 68.0, 67.7,
67.5, 65.4, 63.0, 60.0 (CH2O and CHO), 37.6 (CH2NH), 29.7 (CH2);
FTIR (KBr):
1257, 1118, 1049, 775.
n
(cmꢁ1) ¼ 3335, 2932, 2874, 1787, 1699, 1538, 1446,
NIPU 8; Yield 99%; 1H NMR (DMSO-d6, 400 MHz);
(ppm) ¼ 7.01 (bs, 1.79H, NH(E)), 6.64 (bs, 0.21H, NH(Z)), 4.92 (bs,
d
2H, OH), 4.67 (bs, 0.8H, CHO(CO)N), 4.00e3.75 (m, 2.9H, CH2OCH2),
3.75e3.69 (m, 1.5H, CHOH), 3.69e2.85 (m, 29.8H, CH2O and