Light orange crystals, Yield (2.9 g, 90%), m.p 202-204[degrees]C, IR (KBr, [v.sub.max] in [cm.sup.-1]): 3401 (-NH), 2956 (=C-H), 1891 (C=N), 1610 (C=C), 1644 (C=O), [sup.1]H NMR (DMSO-[d.sub.6], 400 MHz) [delta] ppm: 7.33-7.37 (d, 1H, -C=CH,
vinylic proton, [J.sub.H-H] = 16.4 Hz), 7.48-7.67 (m, 8 aryl, 5 phenyl), 10.2 (s, 1H, -NH of benzimidazole), [sup.13]C NMR (DMSO-[d.sub.6], 100 MHz) d ppm: 102, 106, 108, 110, 112, 120, 121, 122, 128, 129, 130, 132, 142, 148, 152, 190 (12 aryl carbons, 6 phenyl carbons, 2
vinylic carbons, 1 imidazole quaternarycarbon and 1 carbonyl carbon), MS (m/z): 325.2 ([M.sup.+*]), Anal.
(S)-tert-Butyl-3-(acryloyloxy)pyrrolidine-1-carboxylate (12, Method A) was isolated as a pale yellow oil (43.6%); [sup.1]H NMR [delta] 6.30 (d, [delta] = 5.8Hz, [sup.1]H,
vinylic CH); 5.99 (dd, [delta] = 3.5, 5.8Hz, [sup.1]H,
vinylic CH); 5.73 (d, [delta] = 3.5 Hz, [sup.1]H,
vinylic CH); 5.23 (br m, [sup.1]H, ring diastereotopic 4-CH); 3.47 (m, 2H, N-C[H.sub.2]); 3.33 (m, 2H, N-C[H.sub.2]); 1.95 (m, 2H, ring 4-C[H.sub.2]); 1.34 (s, 9H, t-BOC C[H.sub.3]); [sup.13]C NMR [delta] 28.6, 30.9, 31.7, 43.7, 44.12, 51.5, 51.9, 73.3, 74.1, 79.7, 128.4, 131.4, 154.5, and 165.8; IR (film) 3061, 2979, 2885, 1727, 1620, 1479, 1412, 1366, 1297, 1270, 1192, 1117, and 1096 [cm.sup.?1]; EIMS (70 eV): 168 [[M-t-BuO].sup.+], 113 [[[C.sub.5][H.sub.7]N[O.sub.2]].sup.+], and 57 [[t-Bu].sup.+].
[sup.1]H NMR in (DMSO-[d.sub.6]), [delta]: 2.23 (s, 3H,- CHa); 4.89-4.80 (m, 2H, -O-C[H.sub.2]-C[F.sub.3]); 5.55 (s, 2H, -N-C[H.sub.2]-pyridine ring); 7.14-7.18 (d, 1H,
vinylic proton); 7.88 (s, 1H, indole ring protons); 7.67 (d, 1H,
vinylic proton); 7.30-8.23 (m, 8H, Ar-H); 7.40 (d, 1H, pyridine-H); 8.21 (d, 1H, pyridine-H); Mass (m/z): 485 (M+[H.sup.+]).
benzylic = allylic > tertiary carbon > secondary carbon > primary carbon >
vinylic >> phenyl
Also functions as an inhibitor and shortstopping agent for acrylic and
vinylic monomers.
It is a stable white solid that is soluble in a range of organic solvents and copolymerizes with other
vinylic monomers.
The
vinylic proton in the enamine is easily observed as a single peak at 8.81 ppm; signals at higher field belonging to the protons H-4 and 1-OH at [delta] 8.16 and 7.63 ppm, respectively, are coupled.
This carbon atom allows for an attack by different nucleophiles (S- and N-) in nucleophilic
vinylic substitution (SNVin) processes.
Synergy between the highly reactive terminal acrylate functionality and the internal
vinylic structures was evident when compared to binary blends of monomeric diacrylate and poly(butadiene), and may also contribute to the efficiency of the polymeric diacrylate coagent compared to monomeric forms.
This sequence of steps--alkene binding, functionalization, and retrocycloaddition--represents an overall
vinylic C-H functionalization reaction of simple olefins which does not require the use of directing groups.
Besides addition polymerization of
vinylic monomers, Zhou and coworkers, after proper surface modification, performed surface-initiated ring-opening polymerizations of norbornene, lactide, and carprolactone, respectively [34-36].