F. Helmholz et al. · Synthesis of Unsymmetrical Bis(imidoyl)dichlorides of Oxalic Acid
1195
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M. p. 148 C. – IR (KBr): ν = 826 (m), 1443 (w9, 1521 (m), N - ( 3 , 5 - D i m e t h y l p h e n y l ) - N - ( p - t o l y l ) - o x a l -
1666 (s), 3282 (s) cm−1. – 1H NMR (200 MHz, CDCl3): d i i m i d o y l d i c h l o r i d e (4g)
δ = 2.23 (s, 3 H, CH3), 2.34 (s, 3 H, CH3), 6.94 – 7.66 (m, 2
Starting with 3g (10 mmol) and PCl5 (4.16 g, 20 mmol),
H, Ar). – 13C NMR (50 MHz, CDCl3): δ = 17.83, 21.03,
4g was isolated as a yellow solid. – 1H NMR (200 MHz,
118.65, 120.12, 120.35, 126.51, 126.73, 128.95, 129.17,
CDCl3): δ = 2.42 (s, 3 H, CH3), 2.44 (s, 3 H, CH3), 2.48 (s,
129.74, 131.27, 136.47, 136.36, 142.01, 145.79. – MS (EI,
3 H, CH3), 6.82 (s, 2 H, Ar), 6.96 (s, 1 H, Ar), 7.16 – 7.19
70 eV): m/z (%) = 305 ([M]+, 15), 269 (7), 166 (33),
(d, 2 H, Ar), 7.29 – 7.32 (d, 2 H, Ar). – 13C NMR (50 MHz,
138 (36), 77 (44), 28 (100). – C16H14Cl2N2 (305.19):
calcd. C 62.99, H 4.58, N 9.17; found C 63.08, H 4.96,
N 9.09.
CDCl3): δ = 20.91, 21.12, 22.53, 117.68, 119.98, 120.77,
127.95, 129.34, 129.41, 136.58, 136.81, 137.83, 138.46,
142.75, 145.59. C17H16Cl2N2.
N - ( 3 , 5 - D i m e t h y l p h e n y l ) - N’ - p h e n y l - o x a l -
N - ( 2 , 4 - D i m e t h y l p h e n y l ) - N’ - ( p - m e t h o x y -
d i i m i d o y l d i c h l o r i d e (4d)
p h e n y l ) - o x a l d i i m i d o y l d i c h l o r i d e (4h)
Starting with 3d (2.60 g, 10 mmol) and PCl5 (4.16 g,
Starting with 3h (2.90 g, 10 mmol) and PCl5 (4.16 g,
20 mmol), 4d was isolated as a yellow solid. – 1H NMR
20 mmol), 4h (2.20 g, 65%) was isolated as a yellow solid.
(200 MHz, CDCl3): δ = 2.31 (s, 6 H, 2 × CH3), 6.71 (s,
2 H, Ar), 6.86 (s, 1 H, Ar), 7.06 7.09 (d, 2 H, Ar), 7.19 – 7.24
(t, 1 H, Ar), 7.36 – 7.42 (t, 2 H, Ar). – 13C NMR (50 MHz,
CDCl3): δ = 21.17, 22.56, 117.74, 119.58, 120.21, 126.48,
128.04, 128.83, 129.02, 138.55, 138.72, 145.53, 145.63.
C16H14Cl2N2.
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M. p. 56 C. – IR (KBr): ν = 830 (s), 1032 (m), 1249 (s),
1523 (s), 1597 (m), 1665 (s), 3302 (s) cm−1. – 1H NMR
(200 MHz, CDCl3): δ = 2.22 (s, 3 H, CH3), 2.33 (s, 3
H, CH3), 3.83 (s, 3 H, OCH3), 6.90 – 7.08 (m, 5 H, Ar),
7.23 – 7.33 (d, 2 H, Ar). – 13C NMR (50 MHz, CDCl3):
δ = 17.79, 20.98, 55.41, 114.06, 118.61, 123.92, 126.70,
129.41, 131.18, 136.25, 137.83, 137.95, 138.07, 142.28,
158.75, 158.89. – MS (EI, 70 eV): m/z (%) = 335 ([M]+,
59), 300 (41), 168 (1009, 77 (81), 28 (89). – C17H16Cl2N2O
(335.22): calcd. C 60.93, H 4.77, N 8.35; found C 59.60,
H 4.79, N 8.38.
N - ( 1 - N a p h t h y l ) - N’ - p h e n y l - o x a l d i i m i d o y l
c h l o r i d e (4e)
Starting with 3e (2.90 g, 10 mmol) and PCl5 (4.16 g,
20 mmol), 4e (1.85 g, 56%) was isolated as a yellow solid. –
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IR (KBr): ν = 492 (w), 793 (m), 1445 (s), 1501 (s), 1526 (s),
N - ( 3 , 5 - D i m e t h y l p h e n y l ) - N’ - ( p - m e t h o x y -
p h e n y l ) - o x a l d i i m i d o y l d i c h l o r i d e (4i)
1682 (s), 3268 (s). – 1H NMR (200 MHz, CDCl3): δ = 7.15 –
7.17 (d, 1 H, Ar), 7.22 – 7.33 (m, 3 H, Ar), 7.43 – 7.45 (d,
1 H, Ar), 7.48 – 7.62 (m, 4 H, Ar), 7.76 – 7.78 (d, 1 H, Ar),
7.81 – 7.89 (m, 1 H, Ar), 7.96 – 8.05 (m, 1 H, Ar). – 13C NMR
(50 MHz, CDCl3): δ = 115.03, 115.16, 120.34, 120.46,
123.25, 123.32, 125.27 126.47, 126.66, 127.05, 127.97,
129.00, 133.91, 133.94, 138.64, 138.97, 141.77, 145.72. –
C18H12Cl2N2 (327.19): calcd. C 66.09, H 3.66, N 8.56;
found C 65.52, H 3.83, N 8.49.
Starting with 3i (2.90 g, 10 mmol) and PCl5 (4.16 g,
20 mmol), 4i (1.90 g, 57%) was isolated as a yellow solid.
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M. p. 67 C. – IR (KBr): ν = 730 (m), 817 (w), 1038 (w),
1261 (m), 1531 (s), 1664 (s), 3293 (s) cm−1. – 1H NMR
(200 MHz, CDCl3): δ = 2.32 – 2.34 (s, 6 H, 2 × CH3),
3.84 (s, 3 H, OCH3), 6.70 (s, 2 H, Ar), 6.95 (s, 1 H, Ar),
6.97 – 6.98 (d, 2 H, Ar), 7.29 – 7.30 (d, 2 H, Ar). – 13C NMR
(50 MHz, CDCl3): δ = 20.81, 21.30, 55.43, 114.08, 117.74,
120.19, 124.03, 127.98, 128.53, 128.69, 137.86, 138.66,
145.92, 158.91. – MS (EI, 70 eV): m/z (%) = 335 ([M]+,
25), 299 (15), 168 (100), 77 (38). – C17H16Cl2N2O (335.22):
calcd. C 60.43, H 4.77, N 8.35; found C 60.09, H 4.44,
N 8.01.
N - ( p - M e t h o x y p h e n y l ) - N’ - ( p - t o l y l ) - o x a l -
d i i m i d o y l d i c h l o r i d e (4f)
Starting with 3f (2.85 g, 10 mmol) and PCl5 (4.16 g,
20 mmol),◦4f (1.90 g, 59%) was isolated as a yellow solid.
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M. p. 171 C. – IR (KBr): ν = 695 (w), 779 (m), 847 (s),
1027 (m), 1248 (s), 1503 (s), 1657 (s), 3297 (m) cm−1
.
N - ( p - M e t h o x y p h e y n y l ) - N’ - ( p - n i t r o -
p h e n y l ) - o x a l d i i m i d o y l d i c h l o r i d e (4j)
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1H NMR (200 MHz, CDCl3): δ = 2.38 (s, 3 H, CH3),
3.84 (s, 3 H, OCH3), 6.95 – 7.07 (m, 4 H, Ar), 7.22 – 7.31
(m, 4 H, Ar). – 13C NMR (50 MHz, CDCl3): δ = 21.11,
Starting with 3j (3.15 g, 10 mmol) and PCl5 (4.18 g,
55.44, 114.09, 120.77, 120.82, 123.73, 123.85, 129.50, 20 mmol),◦4j (0.80 g, 23%) was isolated as a yellow solid.
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129.74, 136.59, 137.92, 138.11, 143.19, 158.77, 158.89. – M. p. 132 C. – IR (KBr): ν = 778 (m), 860 (m), 1110 (w),
MS (EI, 70 eV): m/z (%) = 321 ([M]+, 42), 285 (16), 1251 (s), 1345 (s), 1505 (s), 1665 (m) cm−1. – 1H NMR
168 (98), 151 (100), 91 (71). – C16H14Cl2N2O (321.19): (200 MHz, CDCl3): δ = 3.85 (s, 3 H, OCH3), 6.98 –
calcd. C 59.85, H 4.36, N 8.72; found: C 59.21, H 4.61, 7.00 (d, 2 H, Ar), 7.12 – 7.14 (d, 2 H, Ar), 7.39 – 7.40 (d,
N 8.60.
2 H, Ar), 8.33 – 8.34 (d, 2 H, Ar). – 13C NMR (50 MHz,
Unauthenticated
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