Arkivoc 2018, vii, 0-0
Bren, V. A. et al.
N-(Anthracen-9-ylmethyl)-2-chloroethanaminium chloride (2). Compound 1a (10 mmol, 2.5 g) was dissolved
in dry CHCl (100 mL) while heating to 45-50 °C, and a solution of fresh SOCl (12.5 mmol, 0.9 mL) in dry CHCl
10 mL) was added to the reaction mixture for 15-20 min with intensive stirring. The reaction mixture was then
3
2
3
(
stirred for 30 min, gradually heated and refluxed for 2 h, and then evaporated to 10-15 mL on a rotary
evaporator. The residue was cooled to 0 °C, the precipitate was filtered, and washed on the filter by cooled
CHCl (2 × 5 mL) and acetone (2 × 5 mL). The resulting hydrochloride was recrystallized to afford the title
3
-1
compound 2. Yield 92% (2.8 g), pale yellow solid, mp 222-223 °C (n-BuOH). IR (ν, cm ): 3320, 3275, 1470,
1
1
365, 1017, 756. H NMR (300 MHz, DMSO-d
): δ
6 H
3.44–3.63 (m, 2H, NCH
2
), 4.00 (t, 2H, J 6.2 Hz, CH Cl), 5.26
2
(
br.s, 2H, CH
2
N), 7.50–7.73 (m, 4H, Ar H), 8.12 (d, 2H, J 8.6 Hz, Ar H), 8.55 (d, 2H, J 8.6 Hz, Ar H), 8.71 (s, 1H, Ar
+
H), 9.85 (br.s, 2H, N H
2
). Anal. calcd. for C17
H
17Cl N: C, 66.68; H, 5.60; Cl, 23.15; N, 4.57. Found: C, 66.75; H,
2
5.55; Cl, 23.08; N, 4.62%.
N-(Anthracen-9-ylmethyl)-3-chloropropan-1-aminium chloride (3) was synthesized at the same manner as
-1
compound 2. Yield 82% (2.6 g), light yellow solid, mp 200-201 °C (n-BuOH). IR (ν, cm ): 3300, 3245, 1465,
1
1
400, 1005, 761. H NMR (300 MHz, DMSO-d
6
): δ
H
1.90-2.05 (m, 2H, CCH
2
C), 3.44 (t, 2H, J 6.2 Hz, CH Cl), 4.14-
2
4
.25 (m, 2H, NCH
2
), 5.18 (s, 2H, CH
2
N), 7.38-7.55 (m, 4H, Ar H), 8.07 (d, 2H, J 8.6 Hz, Ar H), 8.42 (d, 2H, J 8.6 Hz,
+
Ar H), 8.57 (s, 1H, Ar H), 10.11 (br.s, 2H, N H
Found: C, 67.61; H, 6.07; Cl, 22.06; N, 4.46%.
2
). Anal. calcd. for C18
H
19Cl N: C, 67.51; H, 5.98; Cl, 22.14; N, 4.37.
2
N-(Anthracen-9-ylmethyl)-2-chloro-N-(1-phenylethyl)acetamide (4). Amine 1c (10 mmol, 3.1 g) was dissolved
in dry toluene (50 mL) and a solution of chloroacetyl chloride (12.5 mmol, 1.0 mL) in dry pyridine (20 mmol,
1.6 mL) was added with intense stirring. The reaction mixture was refluxed for 6 h, cooled to 5-10 °C and the
precipitate of pyridine hydrochloride was filtered off. The filtrate was washed with water (2 × 20 mL) in a
separating funnel to remove the residue of pyridine hydrochloride. The resulting toluene solution was dried
(Na
2
SO
4
) for 1 h. Then Na
2
SO
4
was filtered off, the solvent was removed on a rotary evaporator, the residue
was recrystallized to afford a yellow precipitate which was filtered, washed with petroleum ether (3 × 10 mL)
-1
and dried to afford the title compound 4. Yield 75% (2.9 g), mp 64-65 °C (n-hexane/PhH, 75:25). IR (ν, cm ):
1
1
625, 1500, 1440, 1022. H NMR (300 MHz, DMSO-d
6
): δ
H
1.45 (d, 3H, J 7.0 Hz, CH
), 7.18–7.60 (m, 9H, Ar H), 7.97-8.20 (m, 3H, Ar H),
22ClNO: C, 77.41; H, 5.72; Cl, 9.14; N, 3.61. Found: C, 77.48; H,
3
), 3.80 (s, 2H, CH Cl), 4.02
2
(d.d, 1H, J
1
5.0 Hz, J
2
16.0 Hz, CH), 5.21 (d, 2H, J 7.2 Hz, NCH
.33 (d, 2H, J 8.8 Hz, Ar H). Anal. calcd. for C25
2
8
H
5.67; Cl, 9.20; N, 3.54%.
N-(Anthracen-9-ylmethyl)-2-chloro-N-(3,5-dichlorophenyl)acetamide (5) was synthesized in the same
manner as 4 from amine 1d and chloroacetyl chloride. Yield 84% (3.6 g), yellow solid, mp 177-178 °C (THF). IR
-1
1
(
ν, cm ): 1620, 1495, 1430, 1240, 1005, 759. H NMR (300 MHz, DMSO-d
): δ
6 H
3.97 (s, 2H, CH
2
Cl), 6.05 (s, 2H,
CH N), 7.11-7.41 (m, 3H, Ar H), 7.46-7.62 (m, 4H, Ar H), 8.03 (d, 2H, J 8.8 Hz, Ar H), 8.46 (d, 2H, J 8.8 Hz, Ar H),
2
8
.60 (s, 1H, Ar H). Anal. calcd. for C24
H
18Cl NO: C, 65.10; H, 4.10; Cl, 24.02; N, 3.16. Found: C, 65.18; H, 4.18; Cl,
3
23.94; N, 3.04%.
N-(Anthracen-9-ylmethyl)-3-chloro-N-(1-phenylethyl)propanamide (6) was synthesized at the same manner
as 4 from amine 1c and 3-chloropropionyl chloride. Yield 70% (2.8 g), light yellow solid, mp 56-57 °С (n-
-
1
1
hexane/PhH, 80:20). IR (ν, cm ): 1630, 1485, 1405, 1009. H NMR (300 MHz, DMSO-d
Hz, CH ), 2.91 (d, 2H, J 6.8 Hz, CCH C), 3.42 (d, 2H, J 6.8 Hz, CH Cl), 3.94 (d.d, 1H, J 5.0 Hz, J
d, 2H, J 6.8 Hz, NCH
NO: C, 64.43; H, 3.76; Cl, 24.81; N, 3.27. Found: C, 64.50; H, 3.68; Cl, 24.90; N, 3.20%.
6
): δ
H
1.42 (d, 3H, J 6.8
15.0 Hz, CH), 5.04
3
2
2
1
2
(
2
), 7.14-7.55 (m, 9H, Ar H), 7.92-8.17 (m, 3H, Ar H), 8.40 (d, 2H, J 8.6 Hz, Ar H). Anal. calcd.
for C25
H
16Cl
3
N-(Anthracen-9-ylmethyl)-3-chloro-N-(3,5-dichlorophenyl)propanamide (7) was synthesized in the same
manner as 4 from amine 1d and 3-chloropropionyl chloride. Yield 80% (3.5 g), light green-yellow solid, mp 172-
-1
1
1
73 °C (n-BuOH). IR (ν, cm ): 1615, 1500, 1430, 1235, 1018, 764. H NMR (300 MHz, DMSO-d
6
): δ 2.96 (d, 2H,
H
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