Aliphatic nitro compounds chemistry: oximes–nitrones tunable production through directed…
4.12–4.19 (m, 2H), 4.25 (t, J = 4.4 Hz, 4H), 6.94 (d,
J=8 Hz, 2H), 7.06–7.10 (m, 2H), 7.37 (t, J=6.8 Hz, 2H),
8.00 (s, 2H), 9.35 (d, J = 8 Hz) ppm; 13C NMR (CDCl3,
100.6 MHz): δ=14.2, 68.2, 69.8, 111.5, 120.4, 121.5, 126.4,
129.0, 131.2, 155.9 ppm; IR (neat): ̄ꢀ = 744, 1086, 1139,
1256, 1457, 2859, 2925, 3051 cm−1.
N, N’‑ [ [ [ [ [ [ O x y b i s ( e t h a n e ‑ 2 , 1 ‑ d i y l ) ] b i s ( o x y ) ] ‑
bis(ethane‑2,1‑diyl)]bis(oxy)]bis(2,1‑phenylene)]‑
bis(methylidyne)]bis(ethanamine oxide) (4k,
1
C26H36N2O7) Yield 78%; yellow oil; H NMR (CDCl3,
400 MHz): δ=1.52 (t, J=7.6 Hz, 6H), 3.66–3.68 (m, 8H),
3.83 (t, J = 4.8 Hz, 4H), 3.96 (q, J = 7.2 Hz, 4H), 4.13 (t,
J=4.8 Hz, 4H), 6.85 (d, J=8 Hz, 2H), 6.98–7.02 (m, 2H),
7.28–7.32 (m, 2H), 7.89 (s, 2H), 9.26 (dd, J= 8, 1.6 Hz,
2H) ppm; 13C NMR (CDCl3, 100.6 MHz): δ = 13.6, 62.3,
68.0, 69.6, 70.7, 111.3, 120.1, 121.1, 128.3, 128.7, 131.4,
156.0 ppm; IR (neat): ̄ꢀ = 739, 1051, 1156, 1250, 1463,
1588, 2927, 3050 cm−1.
N,N’‑[[[[[Ethane‑1,2‑diylbis(oxy)]bis(ethane‑2,1‑diyl)]‑
bis(ox y)]bis(2, 1‑phenylene)]bis(methylidyne)]‑
bis(methanamine oxide) (4g, C22H28N2O6) Yield 73%; yel-
low oil; 1H NMR (CDCl3, 400 MHz): δ=3.76 (s, 4H), 3.88–
3.91 (m, 10H), 4.20 (t, J = 4.8 Hz, 4H), 6.90 (d, J = 8 Hz,
2H), 7.04–7.08 (m, 2H), 7.34–7.38 (m, 2H), 7.87 (s, 2H),
9.26 (dd, J = 7.6, 1.2 Hz, 2H) ppm; 13C NMR (CDCl3,
100.6 MHz): δ=54.8, 68.0, 69.7, 70.8, 111.4, 120.0, 121.2,
128.7, 130.0, 131.6, 156.0 ppm; IR (neat): ̄ꢀ = 753, 1050,
1116, 1163, 1248, 1458, 1587, 2862, 2926 cm−1.
N, N’‑ [ [ [ [ [ [ O x y b i s ( e t h a n e ‑ 2 , 1 ‑ d i y l ) ] b i s ( o x y ) ] ‑
bis(ethane‑2,1‑diyl)]bis(oxy)]bis(2,1‑phenylene)]‑
bis(methylidyne)]bis(propan‑2‑amine oxide) (4l,
1
C28H40N2O7) Yield 79%; yellow oil; H NMR (CDCl3,
400 MHz): δ=1.51 (d, J=6.4 Hz, 12H), 3.71–3.76 (m, 8H),
3.89 (t, J=4.4 Hz, 4H), 4.18 (t, J=4.8 Hz, 4H), 4.22–4.29
(m, 2H), 6.89 (d, J=8 Hz, 2H), 7.02–7.06 (m, 2H), 7.32–
N,N’‑[[[[[Ethane‑1,2‑diylbis(oxy)]bis(ethane‑2,1‑diyl)]‑
bis(ox y)]bis(2, 1‑phenylene)]bis(methylidyne)]‑
bis(ethanamine oxide) (4h, C24H32N2O6) Yield 72%; yellow
oil; 1H NMR (CDCl3, 400 MHz): δ=1.55 (t, J=7.2 Hz, 6H),
3.75 (s, 4H), 3.89 (t, J = 4.4 Hz, 4H), 4.00 (q, J = 7.2 Hz,
4H), 4.19 (t, J=4.4 Hz, 4H), 6.89 (d, J=8.4 Hz, 2H), 7.01–
7.05 (m, 2H), 7.33–7.37 (m, 2H), 7.92 (s, 2H), 9.29 (dd,
J = 8, 1.2 Hz, 2H) ppm; 13C NMR (CDCl3, 100.6 MHz):
δ=13.6, 62.3, 68.0, 69.7, 70.8, 111.3, 120.0, 121.2, 128.6,
128.9, 131.5, 156.1 ppm; IR (neat): ̄ꢀ = 756, 1052, 1157,
1247, 1298, 1462, 1594, 2869, 2928 cm−1.
7.36 (m, 2H), 7.96 (s, 2H), 9.34 (d, J=7.6 Hz, 2H) ppm; 13
C
NMR (CDCl3, 100.6 MHz): δ=20.9, 68.0, 69.7, 70.7, 111.3,
120.3, 121.2, 126.6, 128.9, 131.2, 156.0 ppm; IR (neat):
̄ꢀ =740, 1051, 1101, 1143, 1257, 1364, 1462, 1565, 1593,
2931, 2975, 3052 cm−1.
2‑[2‑[2‑[2‑[2‑[(E)‑(Hydroxyimino)methyl]phenoxy]ethoxy]‑
ethoxy]ethoxy]benzaldehyde oxime (DiOx, C20H24N2O6) The
dialdehyde 2c (0.179 g, 0.5 mmol), 2 g anhydrous Na2CO3,
SnCl2·2H2O (4 mmol), and nitroethane (2 mmol) were
mixed in a round bottom Pyrex fask at refux conditions for
20 h. After the completion of the reaction, the mixture was
extracted with dichloromethane (3×10 cm3). The extracts
were concentrated in a rotary evaporator and the crude mix-
ture was purifed by column chromatography to aford the
N,N’‑[[[[[Ethane‑1,2‑diylbis(oxy)]bis(ethane‑2,1‑diyl)]‑
bis(ox y)]bis(2, 1‑phenylene)]bis(methylidyne)]‑
bis(propan‑2‑amine oxide) (4i, C26H36N2O6) Yield 80%; yel-
low oil; 1H NMR (CDCl3, 400 MHz): δ=1.46 (d, J=6.4 Hz,
12H), 3.73 (s, 4H), 3.87 (t, J = 4.8 Hz, 4H), 4.16 (t,
J=4.4 Hz, 4H), 4.19–4.24 (m, 2H), 6.86 (d, J=8 Hz, 2H),
6.98–7.02 (m, 2H), 7.28–7.32 (m, 2H), 7.93 (s, 2H), 9.31
(d, J = 7.6 Hz, 2H) ppm; 13C NMR (CDCl3, 100.6 MHz):
δ=20.89, 68.0, 69.7, 70.8, 111.3, 120.2, 121.1, 126.6, 128.8,
131.2, 156.0 ppm; IR (neat): ꢀ̄=740, 923, 1051, 1147, 1244,
1303, 1371, 1460, 1566, 1593, 2931, 3049 cm−1.
1
corresponding dioxime. Yield 52%; yellow oil; H NMR
(CDCl3, 400 MHz): δ =3.78 (s, 4H), 3.90 (t, J = 4.8 Hz,
4H), 4.18 (t, J=4.8 Hz, 4H), 6.90–6.97 (m, 4H), 7.29–7.32
(m, 2H), 7.71 (d, 2H), 8.57 (s, 2H), 9.31 (br, 2H) ppm; 13
C
NMR (CDCl3, 100.6 MHz): δ =68.2, 69.7, 70.9, 112.6,
121.1, 126.6, 131.1, 146.4, 156.8 ppm; IR (neat): ̄ꢀ =750,
802, 959, 1050, 1105, 1253, 1366, 1452, 1487, 2958, 3064,
3358 cm−1.
N, N’‑ [ [ [ [ [ [ O x y b i s ( e t h a n e ‑ 2 , 1 ‑ d i y l ) ] b i s ( o x y ) ] ‑
bis(ethane‑2,1‑diyl)]bis(oxy)]bis(2,1‑phenylene)]‑
bis(methylidyne)]bis(methanamine oxide) (4j,
N‑[2‑[2‑[2‑[(E)‑(Hydroxyimino)methyl]phenoxy]ethoxy]‑
benzylidene]ethanamine oxide (3a, C18H20N2O4) Yield
1
C24H32N2O7) Yield 71%; yellow oil; H NMR (CDCl3,
1
400 MHz): δ=3.67–3.71 (m, 8H), 3.84–3.88 (m, 10H), 4.16
(t, J=4.4 Hz, 4H), 6.87 (d, J=8.4 Hz, 2H), 7.01–7.04 (m)
7.29–7.35 (m, 2H), 7.87 (s, 2H), 9.23 (d, J= 6.8 Hz, 2H)
ppm; 13C NMR (CDCl3, 100.6 MHz): δ=54.7, 68.0, 69.6,
70.7, 111.4, 120.0, 121.1, 128.7, 130.3, 131.6, 156.1 ppm;
IR (neat): ̄ꢀ =757, 941, 1049, 1112, 1161, 1246, 1295, 1413,
1453, 1584, 2866, 2923 cm−1.
78%; yellow oil; H NMR (CDCl3, 400 MHz): δ = 1.51
(t, J = 7.2 Hz, 3H), 3.95 (q, J= 7.2 Hz, 2H), 4.41 (s, 4H),
6.935–7.04 (m, 3H), 7.06–7.10 (m, 1H), 7.35–7.42 (m,
2H), 7.79 (dd, J = 7.6, 1.2 Hz, 1H), 7.84 (s, 1H), 8.54 (s,
1H), 9.33 (dd, J = 8, 1.6 Hz, 1H), 9.44 (br, 2H) ppm; 13C
NMR (CDCl3, 100.6 MHz): δ=13.6, 62.3, 67.1, 67.2, 111.3,
112.8, 120.1, 121.5, 121.6, 121.7, 126.8, 128.8, 129.2,
1 3