The Journal of Organic Chemistry
Article
[3-Amino-benzo[de]isoquinolin-(1Z)-yliden]-p-tolyl-amine (10b).
10b was obtained from a solution of p-toluidine (0.10 g, 1.0 mmol) in
5 mL of tetrahydrofuran and n-butyllithium (0.63 mL, 1.0 mmol)
according to the general procedure. 7 (0.12 mg, 1.0 mmol) was
however dissolved in 15 mL of bromobenzene and added to the
reaction mixture. The solution was stirred for 2 h before it was
quenched. Subsequent crystallization from toluene gave 0.13 g (0.5
(vs), 837 (vs), 926 (m), 989 (vs), 1016 (w), 1038 (vw), 1078 (vw),
1126 (w), 1225 (w), 1317 (m), 1352 (vw), 1364 (vw), 1381 (w), 1418
(w), 1437 (m), 1466 (w), 1501 (m), 1528 (vs), 1585 (vw), 1603 (vw),
1636 (s), 1734 (vw), 1987 (vw), 2021 (vw), 2052 (vw), 2168 (vw),
2191 (vw), 2222 (vw), 2326 (vw), 2361 (vw), 2770 (vw), 2814 (vw),
2853 (w), 2951 (vw), 3057 (vw), 3146 (vw), 3157 (vw), 3167 (vw),
1
3310 (vw), 3319 (vw), 3329 (vw) cm−1. H NMR (300.13 MHz,
CDCl3): δ = 2.70 (s, 6 H, CH3), 7.54−7.60 (m, 2 H, CHar), 7.92 (dd,
̃
mmol, 46%) of 10b as red solid (mp 239−240 °C). IR: ν = 653 (m),
4
682 (m), 715 (m), 725 (w), 773 (vs), 785 (w), 810 (m), 840 (m), 856
(m), 881 (vw), 933 (w), 964 (vw), 974 (vw), 1016 (vw), 1029 (w),
1056 (vw), 1074 (vw), 1105 (w), 1116 (w), 1161 (w), 1192 (vw),
1207 (vw), 1230 (w), 1242 (vw), 1307 (m), 1350 (w), 1386 (m),
1435 (m), 1498 (vs), 1527 (vs), 1570 (s), 1585 (w), 1608 (s), 1652
(vs), 1894 (vw), 1951 (vw), 2027 (vw), 2036 (vw), 2085 (vw), 2094
(vw), 2139 (vw), 2162 (vw), 2185 (vw), 2248 (vw), 2360 (vw), 2717
(vw), 2918 (vw), 3018 (w), 3319 (w), 3072 (w), 3055 (w), 3450 (s)
3J = 8.2 Hz, J = 1.0 Hz, 1 H, CHar), 7.98−8.06 (m, 2 H, CHar), 8.49
(dd, 3J = 7.4 Hz, 4J = 1.1 Hz, 1 H, CHar) ppm. 13C NMR (75.48 MHz,
CDCl3): δ = 47.5 (CH3), 121.8 (Cipso), 124.0 (123.96, CHar), 124.0
(123.99, CHar), 124.8 (Cipso), 125.9, 126.8 (CHar), 128.5 (Cipso), 129.7,
131.9 (CHar), 132.6 (Cipso), 150.0, 155.8 (CN) ppm. HRMS (ESI)
m/z: [M + H]+ Calcd for C14H15N4 239.1290. Found 239.1291.
3-(Methyl-phenyl-hydrazono)-3H-benzo[de]isoquinolin-1-yl-
amine (10e). 10e was obtained from a solution of N-methyl-N-
phenylhydrazine (0.96 g, 7.9 mmol) in 20 mL of tetrahydrofuran, n-
butyllithium (4.9 mL, 7.8 mmol), and a solution of 7 (0.90 g, 5.1
mmol) in 130 mL of tetrahydrofuran according to the general
procedure. In this case, the solution of the dinitrile was cooled to −78
°C and the solution of the deprotonated hydrazine was added. The
crude product was purified with flash chromatography (dichloro-
methane/triethylamine, 10:1) twice. The product was solved in
toluene and filtered over Celite. The Celite was washed thoroughly
with toluene; 1.46 g (4.9 mmol, 97%) of 10e as dark purple solid was
obtained (mp 162 °C, decomp.). Rf = 0.51 (dichloromethane/
cm−1. UV−vis (DCM): λAbs (ν
̃
, ε) = 243 nm (41 152 cm−1, 35 238 L
M
−1 cm−1), 349 nm (28 653 cm−1, 16 085 L M−1 cm−1). Fluorescence
(DCM, 10−4 mol/L, λIrradiation = 350 nm): λEm (ν
̃
) = 498 nm (20 080
1
cm−1). H NMR (300.13 MHz, (CD3)2SO): δ = 2.28 (s, 3H, CH3),
6.98−7.09 (m, 4H, CHar), 7.64−7.73 (m, 2H, CHar), 7.45−8.05 (br,
3
4
3
2H, NH2), 8.12 (dd, J = 8.15 Hz, J = 0.8 Hz, 1H), 8.20 (d, J = 8.1
Hz, 1H) 8.28 (d, 3J = 6.8 Hz, 1H), 8.56 (dd, 3J = 7.4, 4J = 1.1 Hz, 1H)
ppm. 13C NMR (75.48 MHz, (CD3)2SO): δ = 20.6 (CH3), 119.6
(Cipso), 123.0 (CHph), 124.4, 126.1, 126.3, 126.9 (CHnaph), 127.3
(Cipso), 128.6 (CHph), 129.0 (Cipso), 129.8 (CHnaph), 130.5 (Cipso),
131.8 (Cipso), 132.3(CHnaph), 154.0, 159.7 (CN) ppm. HRMS (ESI)
m/z: [M + H]+ Calcd for C19H16N3 286.1339. Found 286.1340. Anal.
Calcd for C19H15N3 (M = 285.34): C, 79.98; H, 5.30; N, 14.73. Found:
C, 79.73; H, 5.07; N, 14.49. For X-ray crystal structure data see the
̃
triethylamine = 10:1). IR: ν = 615 (m), 665 (w), 691 (vs), 708 (m),
721 (vw), 750 (vs), 764 (vs), 773 (s), 785 (vs), 799 (vw), 837 (m),
856 (vw), 872 (w), 901 (m), 957 (w), 964 (w), 991 (m), 1026 (m),
1080 (w), 1097 (s), 1155 (vw), 1184 (w), 1202 (vw), 1233 (w), 1290
(s), 1310 (vs), 1350 (w), 1385 (w), 1416 (w), 1435 (m), 1458 (w),
1487 (vs), 1528 (s), 1591 (s), 1641 (vs), 2874 (vw), 2909 (vw), 3046
(1Z)-1-(Pyridin-2-ylimino)-1H-benzo[de]isoquinolin-3-amine
(10c). 10c was obtained from a solution of 2-aminopyridine (1.04 g,
11.0 mmol) in 15 mL of tetrahydrofuran, n-butyllithium (6.9 mL, 11.0
mmol), and a solution of 7 (1.78 g, 10.0 mmol) in 200 mL of
tetrahydrofuran according to the general procedure. The reaction
mixture was refluxed for 5 h and quenched afterward. The crude
product was crystallized twice from toluene, giving 0.27 g (1.5 mmol,
(w, br), 3285 (vw), 3482 (w) cm−1. UV−vis (DCM): λAbs (ν
̃
, ε) = 469
nm (21 322 cm−1, 29 742 L M−1 cm−1). Fluorescence (DCM, 10−4
1
mol/L, λIrradiation = 480 nm): λEm (ν
̃
) = 595 nm (16805 cm−1). H
NMR (300 MHz, CDCl3) δ = 3.36 (s, 3 H, CH3), 6.89 (t, 3J = 7.2 Hz,
1 H, CHar), 7.11−7.20 (m, 2 H, CHar), 7.22−7.34 (m, 2 H, CHar),
7.58 (dd, 3J = 8.2, 7.5 Hz, 1 H, CHar), 7.60−7.67 (m, 1 H, CHar), 7.92
(d, 3J = 7.2 Hz, 1 H, CHar), 7.96 (dd, 3J = 8.2, 4J = 0.8 Hz, 1 H, CHar),
̃
50%) of 10c as red solid (mp 166 °C, decomp.). IR: ν = 617 (w), 679
3
3
4
8.03 (d, J = 7.9 Hz, 1 H, CHar), 8.71 (dd, J = 7.5, J = 1.1 Hz, 1 H,
CHar). 13C NMR (75.47 MHz, (CD3)2SO): δ = 41.0 (CH3), 113.7
(CHph), 117.8 (CHar), 119.9 (Cipso), 123.2 (CHar), 123.5 (CHar), 126.1
(CHar), 126.8 (CHar), 127.1 (Cipso), 127.8 (CHar), 128.5 (CHph), 128.9
(Cipso), 131.5 (CHar), 132.2 (Cipso), 148.7, 151.2, 156.2 (N-Cipso, C
N, CN) ppm. HRMS (ESI) m/z: [M + H]+ Calcd for C19H17N4
301.1448. Found 301.1452. Anal. Calcd for C19H16N4 (300.36): C,
75.98; H, 5.37; N, 18.65. Found: C, 76.00; H, 5.35; N, 18.63.
(vw), 700 (s), 714 (vw), 733 (vs), 770 (vs), 843 (s), 870 (s), 916 (w),
932 (w), 941 (w), 974 (w), 993 (s), 1028 (w), 1049 (w), 1078 (w),
1097 (w), 1128 (m), 1146 (w), 1155 (m), 1165 (w), 1200 (m), 1236
(vs), 1256 (s), 1267 (s), 1279 (m), 1287 (m), 1323 (vs), 1356 (s),
1369 (w), 1387 (m), 1418 (s), 1447 (s), 1464 (vs), 1491 (s), 1522
(vs), 1547 (s), 1566 (s), 1587 (s), 1603 (w), 1626 (m), 1672 (vs),
1711 (vw), 1771 (vw), 3003 (s), 3038 (s), 3225 (w), 3358 (vw) cm−1.
UV−vis (DCM): λAbs (ν
cm−1), 365 nm (27 397 cm−1, 31 554 L M−1 cm−1). Fluorescence
(DCM, 10−4 mol/L, λirradiation = 350 nm): λEm (ν
) = 506 nm (broad,
̃
, ε) = 249 nm (40 160 cm−1, 44 820 L M−1
5-(p-Tolylimino)-5H-dibenzo[c,e]azepin-7-amine (11a). 11a was
obtained from a solution of p-toluidine (0.32 g, 3.0 mmol) in 30 mL of
tetrahydrofuran, n-butyllithium (1.9 mL, 3.0 mmol), and a solution of
8 (0.61 g, 3.0 mmol) in 15 mL of tetrahydrofuran according to the
general procedure. The crude product was crystallized from toluene.
Some unreacted 2,2′-dicyanobiphenyl (8) could be separated from the
filtrate. The residue was purified by flash chromatography (tert-
butylmethyl ether + 5% triethylamine). Subsequent crystallization
from acetonitrile/dichloromethane gave 0.24 g (0.8 mmol, 26%) of
11a as yellow solid (mp 197−199 °C). Rf = 0.43 (tert-butylmethyl
̃
1
3
19763 cm−1). H NMR (400.13 MHz, (CD3)2SO): δ = 6.95 (t, J =
6.1, 2 H, CHar), 7.64 (dt, 3J = 6.8, 4J = 1.7, 1 H, CHar), 7.67−7.79 (m,
2 H, CHar), 8.19 (dd, 3J = 8.1, 4J = 0.8, 1 H, CHar), 8.25 (d, 3J = 8.1, 1
H, CHar), 8.35 (t, 3J = 6.5, 1 H, CHar), 8.59 (dd, 3J = 6.6, 3J = 0.9, 1 H,
CHar) ppm. 13C NMR (100.62 MHz, (CD3)2SO): δ = 117.4 (CHar),
117.7 (Cipso), 119.5 (Cipso), 125.1, 126.2 (CHar), 126.4 (Cipso), 127.0
(126.98), 127.0 (127.01) (CHar), 128.8 (Cipso), 130.7 (CHar), 131.8
(CHar), 132.6 (CHar), 136.6 (CHar), 148.0 (CHar), 155.1, 160.0, 164.2
(CN) ppm. HRMS (ESI) m/z: [M + H]+ Calcd for C17H13N4
273.1135. Found 273.1133. Anal. Calcd for C17H12N4 (272.30): C,
74.98; H, 4.44; N, 20.58. Found: C, 74.61; H, 4.43; N, 20.18. For X-
̃
ether + 5% triethylamine). IR: ν = 615 (w), 669 (m), 687 (m), 712
(vw), 743 (vs), 764 (w), 775 (s), 808 (vs), 841 (vw), 864 (w), 937
(vw), 953 (vw), 986 (vw), 1018 (w), 1034 (w), 1055 (w), 1065 (vw),
1111 (w), 1136 (vw), 1165 (vw), 1179 (vw), 1227 (m), 1261 (w),
1319 (vs), 1379 (w), 1404 (vs), 1437 (m), 1504 (s), 1570 (vs), 1587
(vs), 1628 (s), 1709 (vw), 2336 (vw), 2359 (vw), 2864 (vw), 2916
(vw), 3022 (vw), 3051 (vw), 3063 (vw), 3136 (w), 3258 (vw), 3296
3-(Dimethyl-hydrazono)-3H-benzo[d,e]isoquinolin-1-ylamine
(10d). 10d was obtained from a solution of N,N-dimethylhydrazine
(0.35 mL, 0.27 mg, 4.5 mmol) in 10 mL of tetrahydrofuran, n-
butyllithium (2.80 mL, 4.5 mmol), and a solution of 7 (0.53 g, 3.0
mmol) in 40 mL of tetrahydrofuran according to the general
procedure. The mixture was warmed to 50 °C overnight; 0.39 mg
(2.83 mmol, 94%) of 10d was obtained as red resin. Further
purification was not possible due to the sensitivity of the compound.
1
(vw), 3445 (w) cm−1. H NMR (300.13 MHz, (CD3)2SO): δ = 2.24
(s, 3 H, CH3), 6.72 (d, 3J = 8.1 Hz, 2 H, CHar), 7.03 (d, 3J = 8.1 Hz, 2
H, CHar), 7.15 (s, br, 2 H, NHar), 7.47−7.60 (m, 3 H, CHar), 7.60−
7.71 (m, 2 H, CHar), 7.71−7.81 (m, 3 H, CHar) ppm. 13C NMR (75.47
MHz, CDCl3): δ = 20.5 (CH3), 109.6, 122.6, 127.2, 127.5, 127.9,
128.0, 128.1, 128.6, 129.0, 129.7, 130.7 (CHar), 131.5, 133.0, 134.9,
̃
IR: ν = 613 (vs), 644 (s), 667 (vw), 719 (vw), 770 (vs), 799 (w), 824
L
J. Org. Chem. XXXX, XXX, XXX−XXX