Chemistry Reference
In-Depth Information
Its kinematic viscosity was 926.2 cSt at 40 1C and 63.2 cSt at 100 1C, i.e.,aVI
of 131.0. The density at 24 1C was 1.11 g
cm
3
; the specific gravity 1.1103.
1
H-NMR (CDCl
3
) d (ppm): 5.2 (H-CO- glyceryl unit), 4.36 m (6H), 4.3 m (3H),
3.9 m (2H), 2.3 m (24H), 1.66 m (44H), 1.29 bs (86H), 0.95 (overlapping tri-
plets of terminal methyl groups of butyroyl substituents, 21H) and 0.86 m
(overlapping triplets of methyl groups of triglycerides, 15H).
13
C-NMR
(CDCl
3
) d: 173.24, 173.20, 173.14, 173.10, 172.74, 171.08 (C
¼
Os); 160.0
(-HCO
2
small amount of formate ester); 74.99, 74.90, 74.78, 74.76, 74.69,
74.66, 74.02, 73.75, 73.54, 73.51, 73.15, 73.11, 70.50 (CHO- of the hydroxylated
triglyceride chains); 68.92 (-CHO- of the glyceride backbone); 63.76, 62.09,
60.39 (-CH
2
O- of the glycerol backbone); 33.97, 33.93, 31.88, 31.78, 31.58,
30.76, 30.66 (-CH
2
s- next to carbonyls); 29.66, 29.62, 29.43, 29.36, 29.32,
29.30, 29.23, 29.13, 29.08, 29.04, 29.00, 28.95, 28.93; 25.09, 24.79, 24.73, 20.98
(-CH
2
-); 18.57, 18.55, 18.52, 18.46, 18.41, 17.74 (-CH
2
s- contiguous to
terminal -CH
3
s of butyrate substituents); 14.16, 14.07, 14.04 (-CH
3
s of the
triglycerides); 13.98, 13.95, 13.92, 13.66, 13.64, 13.57 (-CH
3
s of substituents).
10.2.3 Valeroylation of PHMWO
Valeric anhydride (98%, 200.0 g, 1.052 mol) and 4-DMAP (1.0 g) were added
to HMWO (173.9 g, 168.1 mmol). The mixture was stirred and warmed to
40 1C until the hydroxylated groups on the oil had been completely ester-
ified, ca. 24 h. The product mixture was then poured into a saturated
NaHCO
3
solution and stirred until neutralized. The neutralized aqueous
mixture was extracted with ethyl acetate (300 mL
3) and the extract was
treated with a mixture of charcoal and clay as above, filtered and the filtrate
dried over Na
2
SO
4.
The solution was filtered and concentrated under re-
duced pressure to give 224.0 g (78.1% of theoretical). The FT-IR spectrum of
this product n
film
on a NaCl disc cm
1
: 2957 vs, 2931 vs, 2859 s, 1819 w, 1739
vs, 1465 m, 1378 m, 1244 m-s, 1172 s, 1036 s; its kinematic viscosity was
489.4 cSt at 40 1C and 42.2 cSt at 100 1C, i.e., a VI of 136. Its density at 22 1C
was 1.096 g
cm
3
and its specific gravity 1.099.
1
H-NMR (CDCl
3
) d (ppm):
4.30 m (3H), 4.10 m (6H), 3.90 m (2H), 2.44 t (J
¼
7.4 Hz, 7.5 Hz, 3H), 2.30 m
(23H), 1.55 m (45H), 1.30 m (100H), 0.90 (overlapping triplets of terminal
methyls of valeroyl substituents, 24 H), 0.85 (overlapping terminal methyl
groups of triglycerides, 15H).
13
C-NMR (CDCl
3
) d: 178.22, 173.30, 173.26,
173.22, 173.19, 173.13, 172.72, 171.06, 168.54 (C
¼
Os); 160.51 (HCO
2
of for-
mate side-product); 77.27, 74.72 (-CHO-); 68.87 (-CHO- of the triglyceride
backbone); 63.68 (-CH
2
O-), 62.04, 60.33 (-CH
2
O-); 34.93, 34.28, 34.20, 34.16,
34.14, 34.12, 34.07, 34.04, 34.00 (-a-CH
2
- to carbonyls); 33.96, 33.92, 33.84,
33.54 (-CH
2
s- at C11 between hydroxylated C10 and C12 of the linoleyl
chains); 31.14, 31.10, 30.73, 30.64, 29.65, 29.61, 29.57, 29.45, 29.43, 29.35,
29.31, 29.29, 29.22, 29.14, 29.12, 29.07, 29.03, 28.99, 28.94, 28.92, 28.84,
28.78,27.14, 27.10, 27.05, 27.00, 26.93, 26.84, 26.76, 26.53, 26.22, 25.76,
25.28, 25.25, 25.07, 25.05, 25.03, 24.95, 24.82, 24.78, 24.75, 24.72, 22.64,
22.60, 22.47, 22.44, 22.24, 22.15, 21.96, 20.96 (-CH
2
-); 14.15, 14.06, 14.04,
