3050
S.-H. Zhao and Z.-B. Chen
3-Hydroxy-2-methylene-3-(3-nitrophenyl)propanenitrile (15a).[9] Pale
white solid; mp 64–668C. IR (KBr): 3438.8, 2239.6, 1533.3, 1348.1 cm21
.
1H NMR (300 MHz, CDCl3): d ¼ 8.07 (s, 1H), 8.02 (d, J ¼ 8.06 Hz, 1H),
7.58 (d, J ¼ 7.71 Hz, 1H), 7.40 (t, J ¼ 7.71 Hz, 1H), 6.03 (s, 1H), 5.93
(s, 1H), 5.27 (s, 1H), 2.84 (br s, 1H).
3-Hydroxy-2-methylene-3-(3-nitrophenyl)propanoic acid, methyl
easter (15b).[3b] Yellow oil. IR (neat): 3482, 1715.1, 1530.9, 1352 cm21
.
1H NMR (300 MHz, CDCl3): d ¼ 8.19 (t, J ¼ 1.01 Hz, 1H), 8.07 (d,
J ¼ 8.01 Hz, 1H), 7.72 (t, J ¼ 7.81 Hz, 1H), 7.50 (t, J ¼ 7.81 Hz, 1H), 6.38
(s, 1H), 5.94 (s, 1H), 5.63 (s, 1H), 3.77 (s, 3H), 3.55 (br s, 1H).
3-Hydroxy-2-methylene-3-(4-nitrophenyl)propanenitrile (16a). Pale
yellow solid; mp 73.5–748C (lit.[3d] mp 72–758C). IR (KBr): 3424.2,
2865.6, 2229.6 cm21
.
1H NMR (300 MHz, CDCl3): d ¼ 8.26 (d, J ¼
8.56 Hz, 2H), 7.60 (d, J ¼ 8.02 Hz, 2H), 6.18 (1s, 1H), 6.10 (s, 1H), 5.44
(s, 1H), 2.11 (br s, 1H)
3-Hydroxy-2-methylene-3-(4-nitrophenyl)propanoic acid, methyl
easter (16b). Yellow solid; mp 71–738C (lit.[3d] mp 71–738C). IR (KBr):
3510, 2992, 1724, 1634, 1359 cm21. H NMR (300 MHz, CDCl3): d ¼ 8.70
1
(d, J ¼ 8.76 Hz, 2H), 7.56 (d, J ¼ 8.76 Hz, 2H), 6.40 (s, 1H), 5.88 (s, 1H),
5.64 (d, J ¼ 5.87 Hz, 1H), 3.75 (s, 3H), 3.40 (br s, 1H).
3-Hydroxy-2-methylene-3-(4-chloro-3-nitrophenyl)propanenitrile
(17a). Yellow oil. IR (neat): 3429.2, 2875.6, 2229.6, 1537 cm21. H NMR
1
(300 MHz, CDCl3, TMS): d ¼ 7.74 (s, 1H), 7.39 (m, 2H), 6.00 (s, 1H), 5.92
(s, 1H), 5.20 (s, 1H), 3.00 (br s, 1H). 13C NMR (300 MHz, CDCl3):
d ¼ 74.73, 118.67, 126.01, 127.53, 129.72, 133.54, 133.94, 134.61, 142.14,
150.38. Anal. calcd. for C10H7ClN2O3: C, 50.31; H, 2.94; N, 11.74. Found:
C, 50.26; H, 2.91; N, 11.72.
3-Hydroxy-2-methylene-3-(4-chloro-3-nitrophenyl)propanoic acid,
methyl easter (17b). White solid; mp 848C. IR (KBr): 3471.6, 1708.8,
1
1533.3 cm21. H NMR (300 MHz, CDCl3, TMS): d ¼ 7.89 (s, 1H), 7.48–
7.55 (m, 2H), 6.39 (s, 1H), 5.89 (s, 1H), 5.55 (s, 1H), 3.73 (s, 3H), 3.01
(br s, 1H). 13C NMR (300 MHz, CDCl3): d ¼ 54.72, 74.56, 126.04, 128.57,
128.88, 129.90, 133.58, 134.22, 143.01, 144.53, 168.69. Anal. calcd.
for C11H10ClNO5: C, 48.62; H, 3.68; N, 5.16. Found: C, 48.35; H, 3.71;
N, 5.12.
3-Hydroxy-2-methylene-3-(2,4-dichlorophenyl)propanenitrile (18a).
White solid; mp 748C. IR (KBr): 3384.8, 2229.6, 1527.5, 1348.1 cm21
.
1H NMR (300 MHz, CDCl3, TMS): d ¼ 7.55 (d, J ¼ 8.01, 1H), 7.39
(s, 1H), 7.28 (d, J ¼ 7.5, 1H), 6.05 (s, 1H), 5.67 (s, 1H), 3.07 (br s,
1H). 13C NMR (300 MHz, CDCl3): d ¼ 72.55, 118.87, 126.70, 130.38,
131.37, 131.97, 134.09, 135.60, 137.60, 142.58. Anal. calcd. for
C10H7Cl2NO: C, 52.63; H, 3.07; N, 6.14. Found: C, 52.58; H, 3.05; N,
6.12.
3-Hydroxy-2-methylene-3-(4-dichlorophenyl)propanenitrile (19a).[3d]
1
Yellow oil. IR (neat): 3431.1, 2227.5, 1490.9 cm21. H NMR (300 MHz,