Synthesis of new heteroatom substituted naphtho- and benzoquinone compounds
661
(499.74 MHz, CDCl3): δ = 0.8 (t, J = 7.32 Hz, 3H, N-CH2-CH2), 3.3 (t, J = 6.84 Hz, 2H, S-CH2), 3.7
CH3), 1.2–1.4 (m, 2H, CH2), 1.6–1.7 (m, 2H, N-CH2- (t,J = 6.84 Hz, 2H, N-CH2), 3.8 (m, 1H, NH), 7.55
CH2), 2.9 (t, J = 6.81 Hz, 2H, N-CH2-CH2), 3.3 (t, J = (t, J = 5.86 Hz, 1H, Harom), 7.60 (t, J = 5.79 Hz, 1H,
7.81 Hz, 2H, S-CH2), 3.5 (t, J = 6.84 Hz, 2H, N-CH2),
H
arom), 7.85 (dd, J = 5.85 Hz, J = 5.37 Hz, 1H, Harom),
7.50 (t, J = 7.32 Hz, 1H, Harom), 7.55 (t, J = 7.81 Hz, 7.96 ppm (dd, J = 5.86 Hz, J = 5.37 Hz, 1H, Harom).
1H, Harom), 7.85 (dd, J = 6.84 Hz, J = 6.85 Hz, 1H, 13C NMR (125.66 MHz, CDCl3): δ = 12.89 (CH3),
H
arom), 7.95 ppm (dd, J = 7.32 Hz, J = 6.84 Hz, 1H, 19.37 (CH2), 28.68 (NH-CH2-CH2), 31.83 (S-CH2),
arom). 13C NMR (125.66 MHz, CDCl3): δ = 12.89 48.38 (NH-CH2-CH2), 51.63 (NH-CH2), 124.80,
H
(CH3), 19.08 (CH2), 23.45 (N-CH2-CH2), 30.28 (S- 125.94, 126.00, 131.51, 131.84, 132.64 (CHarom,Carom),
CH2), 49.17 (N-CH2-CH2), 54.22 (N-CH2), 120.38, 139.07 (=C-S), 145.32 (=C-Cl), 179.24, 182.21 ppm
124.57, 125.52, 131.18, 131.30, 131.56 (CHarom, Carom), (C=O). MS[+ESI]: m/z 325 [M]+ Anal. Calcd. for
132.26 (=C-S), 145.13 (=C-N), 176.80, 178.82 ppm C16H18O2S1N1Cl1 (M, 323.84): C, 59.34; H, 5.60; N,
(C=O). MS[+ESI]: m/z 288 [M]+, 232 [M−56]+. 4.32; S, 9.90. Found: C, 59.40; H, 5.48; N, 4.55, S, 9.78.
Anal. Calcd. for C16H17O2S1N1 (M, 287.38): C, 66.87;
H, 5.96; N, 4.87; S, 11.15. Found: C, 64.40; H, 5.88;
N, 4.85; S, 11.18.
2.5f 2,3,4,5,6,7,8,9-Octahydronaphtho[2,3-e][1,10]
dithionine-11,16-dione (10): Compound 10 was
obtained from the reaction of 1 (1 g, 4.4 mmol) with
9 (0.78 g, 4.4 mmol) according to method 1. Orange
solid. M.p.: 170–171◦C. Yield: 0.52 g (35%). Rf :
0.65 (CHCl3). IR (KBr pellet, cm−1): 3068 (Ar-H),
2930, 2897, 2850 (C-H), 1665 (C=O), 1594 (C=C).
1H NMR (499.74 MHz, CDCl3): δ = 1.1–1.2 (m, 8H,
CH2), 1.6 (m, 4H, S-CH2-CH2), 3.2 (t, J = 5.86 Hz,
4H, S-CH2), 7.65 (dd, J = 5.37 Hz, J = 6.84 Hz, 2H,
2.5d [2-(Butylamino)ethanesulphanyl][2,2ꢁ]-dichloro[3,
3ꢁ]-bis(1,4-naphthoquinone) (7): Compound 7 was
synthesized from the reaction of 1 (1 g, 4.4 mmol)
with 5 (0.58 g, 4.4 mmol) according to method 1.
Black solid. M.p.: 97–98◦C. Yield: 1.1 g (48%). Rf :
0.40 (EtAc). IR (KBr pellet, cm−1): 3069 (Ar-H),
2957, 2928, 2871 (C-H), 1662 (C=O), 1592, 1556
1
(C=C). H NMR (499.74 MHz, CDCl3): δ = 0.9 (t,
H
arom), 8.05 ppm (dd, J = 7.32 Hz, J = 6.84 Hz, 2H,
arom). 13C NMR (125.66 MHz, CDCl3): δ = 21.96,
J = 7.32 Hz, 3H, CH3), 1.1–1.4 (m, 2H, CH2), 1.6–
1.7 (m, 2H, N-CH2-CH2), 3.0 (t, J = 6.81 Hz, 2H,
N-CH2-CH2), 3.8 (t, J = 7.32 Hz, 2H, S-CH2), 4.1
(t, J = 6.84 Hz, 2H, N-CH2), 7.50 (t, J = 5.84 Hz,
1H, Harom), 7.65 (t, J = 6.83 Hz, 1H, Harom), 7.95
(dd, J = 5.32 Hz, J = 5.85 Hz, 1H, Harom), 8.10 ppm
(dd, J = 5.32 Hz, J = 5.84 Hz, 1H, Harom). 13C NMR
(125.66 MHz, CDCl3): δ = 12.70 (CH3), 18.81 (CH2),
22.78 (N-CH2-CH2), 29.39 (S-CH2), 43.72 (N-CH2-
CH2), 67.18 (N-CH2), 125.77, 125.84, 127.80, 131.33,
H
24.19 (CH2), 26.62 (S-CH2-CH2), 35.41 (S-CH2),
126.21, 132.09, 132.60 (CHarom,
C
arom), 149.99 (=C-S),
177.63 ppm (C=O). MS [+ESI]: m/z 333 [M]+. Anal.
Calcd. for C18H20O2S2 (M, 332.48): C, 65.02; H, 6.06;
S, 19.28. Found: C, 65.10; H, 6.36; S, 19.13.
2.5g 7,8,9,10,11,12,13,14,23,24,25,26,27,28,29,30-
Hexadecahydrodinaphtho[2,3-e:2ꢁ,3ꢁ-n] [1,10,13,22]
131.51, 131.87 (CHarom,
Carom), 133.90 (=C-S), 143.29
tetrathiacyclotetracosine-5,16,21,32-tetrone
(11):
(=C–Cl), 148.89 (=C-N), 179.60, 183.43 ppm (C=O).
MS[+ESI]: m/z 478 [M−37]+, 441 [M−73]+. Anal.
Calcd. for C26H21O4S2N1Cl2 (M, 514.43): C, 60.70; H,
4.11; N, 2.72; S, 12.46 Found: C, 60.68; H, 4.08; N,
2.65, S, 12.28.
Compound 11 was obtained from the reaction of 1
(1 g, 4.4 mmol) with 9 (0.78 g, 4.4 mmol) according to
method 1. Red solid. M.p.: 134–135◦C. Yield: 1.4 g
(48%). Rf : 0.48 (CHCl3). IR (KBr pellet, cm−1): 3069
(Ar-H), 2923, 2851 (C-H), 1654 (C=O), 1590, 1454
(C=C). 1H NMR (499.74 MHz, CDCl3): δ = 1.2–1.40
(m, 16H, CH2), 1.4–1.6 (m, 8H, S-CH2-CH2), 3.2 (t,
J = 7.32 Hz, 8H, S-CH2), 7.60 (dd, J = 5.85 Hz, J =
5.37 Hz, 4H, Harom), 7.95 ppm (dd, J = 5.85 Hz, J =
5.86 Hz, 4H, Harom). 13C NMR (125.66 Hz, CDCl3):
δ 27.36, 27.82 (CH2), 29.27 (S-CH2-CH2), 34.00 (S-
CH2), 125.85, 132.05, 132.41 (CHarom, Carom), 147.00
(=C-S), 177.95 ppm (C=O). MS [+ESI]: m/z 665
[M]+. Anal. Calcd. for C36H40S4O4 (M, 664.97): C,
65.02; H, 6.06; S, 19.28. Found: C, 65.05; H, 6.10; S,
19.25.
2.5e 2-[2-(Butylamino)ethanesulphanyl]-3-chloro-1,
4-naphthoquinone (8): Compound 8 was synthesized
from the reaction of 1 (1 g, 4.4 mmol) with 5 (0.58 g,
4.4 mmol) according to method 1. Black solid. M.p.:
110–111◦C. Yield: 0.3 g (21%). Rf : 0.45 (CH2Cl2).
IR (KBr pellet, cm−1): 3344 (NH), 3068 (Ar-H),
2956, 2929, 2870 (C-H), 1659 (C=O), 1591, 1557
1
(C=C). H NMR (499.74 MHz, CDCl3): δ = 0.8 (t,
J = 7.32 Hz, 3H, CH3), 1.1–1.5 (m, 2H, CH2), 1.6–
1.7 (m, 2H, N-CH2-CH2), 3.1 (t, J = 7.81 Hz, 2H,