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H. Neumann et al. · A New Efficient Synthesis of Substituted Luminols
5-Amino-6,8-diethyl-2,3-dihydrophthalazine-1,4-dione (3c)
MS (EI, 70 eV): m/z (%) = 261 (100) [M+], 246 (87) [M+-
NH], 229 (56), 215 (21), 201 (13), 185 (21), 173 (43), 158
(15), 143 (17), 130 (17), 115 (15), 91 (11), 77 (11), 41 (11). –
HRMS (C14H19N3O2): calcd. 261.14774, found 261.14733.
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Yield: 74%; m. p. 281 – 282 C. – IR (KBr): ν = 3476
(s, NH), 3307 (s, NH), 2965 (b), 1630 (s, C=O), 1602 (s),
1567 (s), 1537 (s), 1492 (s), 1457 (w), 1441 (w), 1422 (m),
1329 (s), 1235 (m), 1195 (m), 1068 (w), 1041 (w), 906 (m),
894 (m), 854 (s), 802 (w), 662 (w), 501 (w) cm−1. – 1H NMR
(400.13 MHz, [D6]-DMSO): δ = 11.02 (s, broad, 2 H, NH-
NH), 7.21 (s, broad, 2H, NH2), 7.15 (s, 1 H, CH), 2.93 (q,
J = 7.3 Hz, 2 H, CH2), 2.47 (q, J = 7.5 Hz, 2H, CH2), 1.11
(t, J = 7.3 Hz, 3 H, CH3), 1.06 (t, J = 7.5 Hz, 3 H, CH3). –
13C NMR (100.63 MHz, [D6]-DMSO): δ = 161.85/152.80
(2 C=O), 146.86, 129.93, 128.13, 121.80, 110.87 (5 C),
135.97 (CH), 27.69, 23.33 (2 CH2), 17.59, 12.47 (2 Me). –
MS (EI, 70 eV): m/z (%) = 233 (53) [M+], 218 (100) [M+-
NH], 132 (7), 117 (6), 91 (5). – C12H15N3O2 (233.27): calcd.
C 61.79, H 6.48, N 18.01; found C 61.49, H 6.55, N 18.02.
5-Amino-6,8-dibenzyl-2,3-dihydrophthalazine-1,4-dione
(3e)
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Yield: 81%; m. p. 278-280 C. – IR (KBr): ν = 3473 (s,
NH), 3315 (s,NH), 3026 s, 2900 (b), 1631 (s), 1619 (s),
1571 (s), 1535 (m), 1492 (s), 1452 (m), 1422 (m), 1394 (m),
1322 (s), 1251 (m), 878 (m), 799 (m), 746 (s), 697 (s)
cm−1. – 1H NMR (400.13 MHz, [D6]-DMSO): δ = 11.16
(s, broad, 2 H, NH-NH), 7.37 (s, broad, 2H, NH2),7.26 (m,
2 H, CH), 7.18 (m, 6 H, CH), 7.07 (m, 1 H, CH), 7.01
(d, J = 7.00 Hz, 2 H, CH), 4.38 (s, 2H, CH2), 3.89 (s,
2 H, CH2). – 13C NMR (100.63 MHz, [D6]-DMSO): δ =
161.70/151.64 (2 C=O), 147.45, 127.29, 123.78, 123.02,
111.39 (5 C), 142.82, 138.95 (2 i-CH), 139.24 (CH, phenyl),
128.68, 128.35, 128.11, 128.01 (4 o-CH, 4 m-CH), 126.13,
125.26 (2 p-CH), 38.96, 35.96 (2 CH2). – MS (EI, 70 eV):
m/z (%) = 357 (100) [M+], 280 (12) [M+-Ph], 266 (15)
[M+-Bn], 180 (7), 165 (5), 91 (15). – C22H19N3O2 (357.41):
calcd. C 73.93, H 5.36, N 11.76; found C 73.52, H 5.37,
N 11.52.
5-Amino-6,8-diisopropyl-2,3-dihydrophthalazine-1,4-dione
(3d)
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Yield: 58%; m. p. 224 – 227 C. – IR (KBr): ν = 3481
(s, NH), 3300 (s, NH), 2960 (b), 1649 (s, C=O), 1594 (m),
1569 (s), 1489 (s), 1427 (w), 1399 (w), 1380 (w), 1335 (s),
1301 (s), 1249 (m), 1192 (w), 1092 (w), 1055 (w), 998 (w),
992 (w), 855 (w), 827 (m), 806 (w), 781 (w), 704 (w),
661 (w), 560 (w) cm−1. – 1H NMR (400.13 MHz, [D6]-
DMSO): δ = 11.09 (s, broad, 2 H, NH-NH), 7.43 (s, 1 H,
CH. arom.), 7.39 (s, broad, 2H, NH2), 4.39 (sept, J = 6.9 Hz,
1 H, CHMe2), 3.06 (sept, J = 6.7 Hz, 1H, CHMe2), 1.18
(d, J = 6.7 Hz, 6 H, CHMe2), 1.15 (d, J = 6.9 Hz, 6 H,
CHMe2). – 13C NMR (100.63 MHz, [D6]-DMSO): δ =
161.94/152.99 (2 C=O), 146.18, 134.11, 132.76, 121.30,
110.63 (5 C), 127.94 (CH arom.), 27.62, 26.31 (2 CHMe2),
24.58, 21.84 (2 CHMe2). – MS (EI, 70 eV): m/z (%) =
261 (36) [M+], 246 (100) [M+-NH], 232 (5). – HRMS
(C14H19N3O2): calcd. 261.14774, found 261.14661.
5-Amino-7,8-dihydro-11-thia-7,8-diazabenzo[b]fluorene-
6,9-dione (3f)
Yield: 90%; m.p. > 350 ◦C. – IR (KBr): ν = 3300 (NH),
3052 (b), 1645 (s, C=O), 1589 (s), 1483 (m), 1430 (m),
1407 (m), 1346 (m), 1310 (m), 1262 (w), 1216 (w), 1187 (w),
1087 (w), 1063 (w), 992 (w), 820 (m), 761 (m), 732 (s),
706 (m), 672 (w), 627 (w), 561 (w) cm−1. – 1H NMR
(400.13 MHz, [D6]-DMSO): δ = 11.33 (s, broad, 2 H,
NH-NH), 8.44 (d, J = 8.13 Hz, 1 H, o-CH), 8.10 (d,
J = 7.73 Hz, 1 H, o-CH), 8.00 (s, 1 H, CH), 7.83 (s,
broad, 2 H, NH2), 7.57 (m, 2 H, m-CH). – 13C NMR
(100.63 MHz, [D6]-DMSO): δ = 161.61/152.02 (2 C=O),
145.59, 139.58, 139.28, 135.35, 125.27, 123.89, 106.89
(7 C), 128.37, 125.24, 123.40, 123.24, 103.93 (5 CH). – MS
(EI, 70 eV): m/z (%) = 283 (100) [M+], 268 (7) [M+-NH],
225 (8), 197 (43) [M+-2CO-2NH], 171 (8), 126 (8). HRMS
(C14H9N3O2S): calcd. 283.04153; found 283.04230.
2,4-Diamino-5,7-diisopropylisoindole-1,3-dione (4d)
SiO2 chromatography (heptane/EtOAc 3:1): Rf = 0.11. –
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Yield: 42%; m. p. 133 – 135 C. – IR (KBr): ν = 3462 (s,
NH), 3360 (s, NH), 2963 (s), 2870 (s), 1746 (s), 1703 (s, CO),
1637 (s), 1610 (s), 1487 (s), 1426 (m), 1365 (m), 1288 (w),
1241 (m), 1188 (w), 1166 (w), 1130 (w), 1050 (m), 1007 (w),
901 (w), 880 (w), 799 (w), 759 (m), 655 (w), 633 (w),
586 (w) cm−1. – 1H NMR (400.13 MHz, [D6]-DMSO):
δ = 7.29 (s, 1 H, CH. arom.), 6.18 (s, 2 H, C-NH2), 4.74
(s, 2H, N-NH2), 3.83 (sept, J = 6.9 Hz, 1 H, CHMe2), 3.10
5-Amino-6,8-diphenyl-2,3-dihydrophthalazine-1,4-dione
(3g)
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Yield: 81%; m. p. 266 C. – IR (KBr): ν = 3484 (m),
(sept, J = 6.7 Hz, 1H, CHMe2), 1.18 (d, J = 6.7 Hz, 6 H, 3301 (m), 3160 (s), 3025 (vs, br), 2675 (m), 1648 (vs),
CHMe2), 1.15 (d, J = 6.9 Hz, 6 H, CHMe2). – 13C NMR 1588 (s), 1562 (s), 1484 (vs), 1445 (s), 1377 (m), 1305
(100.63 MHz, [D6]-DMSO): δ = 168.91/167.53 (2 C=O), (vs), 1240 (w), 1202 (w), 1081 (m), 1060 (w), 1025 (w),
142.17, 140.62, 136.04, 122.48, 107.54 (5 C), 128.12 (CH 962 (vw), 912 (vw), 871 (w), 825 (s), 808 (m), 786 (m),
arom.), 26.79, 26.46 (2 CHMe2), 22.80, 22.06 (2 CHMe2). – 760 (m), 700 (vs), 671 (m), 635+(vw), 608 (vw), 583 (m),
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