Journal of the Iranian Chemical Society
(br.s, 2H, OCH2), 4.59 (br.s, 2H, NCH2), 5.49, 5.56 (2 s,
1H, HC4-pyran and HC2-pyran; due to 1,3-proton shift, in
ratio 23%:77%), 7.08–8.11 (m, 10H, Ar–H), 8.86 (br.s, 1H,
NH, exchangeable by D2O). MS (m/z, %): 379 (M+.+2, 30),
378 (M+.+1, 26), 377 (M+., 69), 332 (100). Anal. Calcd. for
C22H16ClNO3 (377.82): C, 69.94; H, 4.27; N, 3.71. Found:
C, 69.85; H, 4.01; N, 3.65.
S y n t h e s i s o f 1 ‑ ( 2 ‑ C h l o r o p h e n y l ) ‑ 3 ‑ h y d r a ‑
zono‑2,3‑dihydrobenzo[f]quinolin‑4(1H)‑amine (10) A mix-
ture of benzo[f]chromeneone 8 (1.54 g, 5 mmol) and excess
hydrazine hydrate (0.5 mL, 10 mmol) in benzene (10 mL)
was stirred at room temperature for 45 min. The deposited
solid was fltered of, dried, and crystallized from ethanol to
give 10 as white crystals, Yield 1377 mg (82%), mp 234–
236 °C. IR spectrum, ν, cm−1: 3327, 3280, 1646, 1627. 1H
NMR spectrum, δ, ppm (J, Hz): 2.98–3.00 and 3.08–3.11
(2 d, 2H, CH2, J = 6, 9), 4.07 (s, 2H, NH2, exchangeable
by D2O), 5.58–5.56 (t, 1H, HC4-pyran, J=3.0), 7.07–8.12
(m, 10H, Ar–H), 9.04, 9.49 (2 s, 2H, NH2, exchangeable by
D2O). MS (m/z, %): 337 (M+.+1, 14), 336 (M+., 28), 304
(100). Anal. Calcd. for C19H17ClN4 (336.82): C, 67.75; H,
5.09; N, 16.63. Found: C, 67.65; H, 5.19; N, 16.53.
Synthesis of 13‑(2‑Chlorophenyl)‑8,10,11,13‑tetrahyd‑
robenzo[5, 6]chromeno[2,3‑e][1, 4]diazepin‑12(9H)‑one
(6) A mixture of compound 2 (1.67 g, 5 mmol), and eth-
ylenediamine (0.28 mL, 5 mmol) in dioxane (10 mL) was
heated under refux for 2 h. The deposited solid on hot was
fltered of, dried, and crystallized from dioxane to give 6
as white crystals, Yield 1146 mg (61%), mp> 300 °C. IR
spectrum, ν, cm−1: 3360, 1684. 1H NMR spectrum, δ, ppm
(J, Hz): 3.48–3.61 (m, 4H, 2NCH2), 5.57, 5.82 (2 s, 1H, Ha,
HC4-pyran and Hb, HC2-pyran, due to 1,3-H shift, in ratio
1:1), 6.99–8.16 (m, 10H, Ar–H), 7.3 (s, 1H, NH, exchange-
able by D2O), 8.18 (s, 1H, CONH, exchangeable by D2O).
MS (m/z, %): 377 (M+., 86), 315 (100). Anal. Calcd. for
C22H17ClN2O2 (376.84):C, 70.12; H, 4.55; N, 7.43. Found:
C, 70.22; H, 4.65; N, 7.33.
Synthesis of 11‑(2‑Chlorophenyl)‑1,2,3,11‑tetrahydrobenz
o[f]imidazo[1,2‑a]quinoline (11) A mixture of benzo[f]
chromeneone 8 (1.54 g, 5 mmol) and ethylenediamine
(0.28 mL, 5 mmol) in dioxane (10 mL) was heated under
refux for 45 min. The deposited solid while heating was
fltered of, dried, and crystallized from dioxane to give 11
as white crystals, Yield 929 mg (56%), mp 182–183 °C.
1
IR spectrum, ν, cm−1: 3352, 1626. H NMR spectrum, δ,
Synthesis of 15‑(2‑Chlorophenyl)‑8,15‑dihydrobenzo[b]
benzo[5, 6]chromeno[2,3‑e][1, 4]diazepin‑14(13H)‑one (7) A
mixture of compound 2 (1.67 g, 5 mmol), and o-phenylen-
ediamine (0.54 g, 5 mmol) in dioxane (10 mL) was heated
under refux for 6 h. The reaction mixture was concentrated
and the solid formed was fltered of, dried, and crystallized
from Ethanol/dioxane to give 7 as white crystals, Yield
ppm (J, Hz): 2.82–2.98 (m, 2H, NHCH2), 3.00–3.10 (m,
3H, NCH2+NH(exchangeable by D2O)), 5.52 (d, 1H, HC4-
pyran, J=6.0), 7.09–8.06 (m, 11H, 10 Ar–H+C=CH). MS
(m/z, %): 333 (M+.+1, 76), 331 (M+.− 1, 20), 331 (100).
Anal. Calcd. for C21H17ClN2 (332.83): C, 75.78; H, 5.15;
N, 8.42. Found: C, 75.84; H, 5.02; N, 8.31.
742 mg (35%), mp 272–274 °C. IR spectrum, ν, cm−1
:
Synthesis of 12‑(2‑Chlorophenyl)‑12H‑benzo[5, 6]
chromeno[2,3‑d]pyrimidin‑11‑amine (12) A mixture of the
enaminonitrile 1 (1.66 g, 5 mmol) and formamide (15 mL)
was heated under refux for 1 h. The deposited solid formed
while refux was fltered of dried, and then crystallized from
dioxane to give 12, as white crystal, Yield 1579 mg (88%),
1
3186, 3136, 1724, 1704. H NMR spectrum, δ, ppm (J,
Hz): 5.68, 5.92 (s, 1H, Ha, HC4-pyran and Hb, HC2-pyran,
due to 1,3-H-shift, in ratio 58%:42%), 6.99–7.97 (m, 14H,
Ar–H), 8.00 (s, 1H, NH, exchangeable by D2O), 11.22 (s,
1H, CONH, exchangeable by D2O). MS (m/z, %): 425 (M+.,
8), 331 (100). Anal. Calcd. for C26H17ClN2O2 (424.88): C,
73.50; H, 4.03; N, 6.59. Found: C, 73.40; H, 4.25; N, 6.51.
1
mp>300 °C. IR spectrum, ν, cm−1: 3468, 3303, 1642. H
NMR spectrum, δ, ppm (J, Hz): 6.12 (s, 1H, HC4-pyran),
6.78 (s, 2H, NH2, exchangeable with D2O), 7.17–7.99
(m, 10H, 10Ar–H), 8.14 (s, 1H, pyrimidine-H). MS (m/z,
%): 361 (M+.+2, 28), 360 (M+.+1, 100). Anal. Calcd. for
C21H14ClN3O (359.81): C, 70.10; H, 3.92; N, 11.68. Found:
C, 70.20; H, 3.72; N, 11.75.
Synthesis of 1‑(2‑Chlorophenyl)‑1,2‑dihydro‑3H‑benzo[f]
chromen‑3‑one (9) A mixture of the enaminonitrile 1
(1.66 g, 5 mmol), acetic acid (10 mL) and fused sodium
acetate (2.00 g) was refuxed for 6 h. The reaction mixture
was allowed to cool, poured onto ice-cold water and stirred
for 5 min. The precipitated solid was fltered of, dried, and
crystallized from ethanol to give 9 as beige crystals, Yield
Synthesis of N‑Acetyl‑N‑(12‑(2‑chlorophenyl)‑12H‑benzo[5,
6]chromeno[2,3‑d]pyrimidine‑11‑yl)acetamide (13) Ami-
nopyrimidine 12 (1.79 g, 5 mol) was heated under refux in
freshly distilled acetic anhydride (10 mL) for 6 h. The excess
acetic anhydride was distilled of. The precipitated solid was
fltered of, dried and then crystallized from ethanol/dioxane
to give 13 as beige crystals, Yield 1484 mg (67%), mp 236–
237 °C. IR spectrum, ν, cm−1: 1729, 1704. MS (m/z, %): 445
1370 mg (89%), mp 164–166 °C. IR spectrum, ν, cm−1
:
1769. 1H NMR spectrum, δ, ppm (J, Hz): 3.20 (d, 2H, CH2,
J=6.0), 5.45 (t, 1H, C4-pyran, J=3.0), 6.71–7.92 (m, 10H,
Ar–H). MS (m/z, %): 309 (M+.+1, 15), 308 (M+., 11), 231
(100). Anal. Calcd. for C19H13ClO2 (308.76):C, 73.91; H,
4.24. Found: C, 73.98; H, 4.36.
1 3