PAPER
Preparation of Polycyclic Azaarenes
2161
N-(2,2-Dimethoxyethyl)-N-(1-naphthylmethyl)toluenesulfon-
amide (11)
Anal. Calcd for C24H29NO4S: C, 67.42; H, 6.84; N, 3.27. Found: C,
67.56; H, 7.07; N, 3.10.
Fine white crystals (PE–toluene, 19:1); yield from aldehyde: 56%;
mp 85–86 °C.
N-(2,2-Dimethoxyethyl)-N-(9-phenanthrylmethyl)toluene-
sulfonamide (18)
White crystals (PE–EtOAc, 1:1); yield from aldehyde: 75%; mp
1H NMR (CDCl3): d = 8.21 (dd, J = 8, 0.5 Hz, 1 H, H-8), 7.85 (dd,
J = 8, 0.5 Hz, 1 H, H-5), 7.79 (superimposed d, J = 8 Hz, 1 H and
d, J = 8 Hz, 2 H, H-2 and tosyl H-2,6), 7.51 (m, 2 H, H-6 and H-7),
7.39–7.32 (m, 2 H, H-3 and H-4), 7.33 (d, J = 8 Hz, 2 H, tosyl H-
3,5), 4.86 (s, 2 H, ArCH2N), 4.12 (t, J = 5 Hz, 1 H, CHCH2), 3.18
(d, J = 5 Hz, 2 H, CHCH2), 3.02 (s, 6 H, 2 OCH3), 2.45 (s, 3 H, tosyl
CH3).
117–118 °C.
1H NMR (CDCl3): d = 8.70 (dd, J = 8, 2 Hz, 1 H, H-4 or H-5), 8.64
(dd, J = 8, 1 Hz, 1 H, H-5 or H-4), 8.23 (dd, J = 8, 2 Hz, 1 H, H-8),
7.79 (d, J = 8 Hz, 2 H, tosyl H-2,6), 7.71–7.53 (m, 5 H, H-1,2,3,6,7),
7.47 (s, 1 H, H-10), 7.31 (d, J = 8 Hz, 2 H, tosyl H-3,5), 4.93 (s, 2
H, ArCH2N), 4.27 (t, J = 5 Hz, 1 H, CHCH2), 3.27 (d, J = 5 Hz, 2
H, CHCH2), 3.05 (s, 6 H, 2 OCH3), 2.44 (s, 3 H, tosyl CH3).
MS (EI): m/z (%) = 399 (1, [M]+), 336, 244, 141, 115, 76, 75 (100).
Anal. Calcd for C22H25NO4S: C, 66.14; H, 6.31; N, 3.51. Found: C,
66.41; H, 6.48; N, 3.79.
MS (EI): m/z (%) = 449 (2, [M]+), 294, 192, 189, 75 (100).
Anal. Calcd for C26H27NO4S: C, 69.46; H, 6.05; N, 3.12. Found: C,
69.51; H, 6.22; N, 3.15.
N-(2,2-Diethoxyethyl)-N-(1-naphthylmethyl)toluenesulfon-
amide (12)
Colorless crystals (PE–toluene, 19:1); yield from aldehyde: 60%;
N-(2,2-Dimethoxyethyl)-N-(1-pyrenylmethyl)toluenesulfon-
mp 87.5–88.5 °C.
amide (24)
Off-white crystals (toluene–Et2O, 1:1); yield from aldehyde: 97%;
mp 133–137 °C.
1H NMR (CDCl3): d = 8.17 (d, J = 8 Hz, 1 H, H-8), 7.84 (d, J = 8
Hz, 1 H, H-5), 7.78 (superimposed d, J = 8 Hz, 1 H, and d, J = 8 Hz,
2 H, H-2 and tosyl H-2,6), 7.49 (m, 2 H, H-6 and H-7), 7.36–7.33
(m, 2 H, H-3 and H-4), 7.32 (d, J = 8 Hz, 2 H, tosyl H-3,5), 4.91 (s,
2 H, ArCH2N), 4.36 (t, J = 5 Hz, 1 H, CHCH2), 3.43 and 3.17 (each
dq, J = 9, 7 Hz, each 2 H, 2 OCHaHbCH3), 3.20 (d, J = 5 Hz, 2 H,
CHCH2), 2.44 (s, 3 H, tosyl CH3), 0.96 (t, J = 7 Hz, 6 H, 2
OCH2CH3).
1H NMR (CDCl3): d = 8.44 (d, J = 9 Hz, 1 H, H-10), 8.21 and 8.19
(2 d, each J = 8 Hz, each 1 H, H-6 and H-8), 8.13 (d, J = 9 Hz, 1 H,
H-9), 8.09 (d, J = 8 Hz, 1 H, H-3), 8.07 (d, J = 9 Hz, 1 H, H-4), 8.04
(d, J = 9 Hz, 1 H, H-5), 8.02 (t, J = 8 Hz, 1 H, H-7), 7.92 (d, J = 8
Hz, 1 H, H-2), 7.78 (d, J = 8 Hz, 2 H, tosyl H-2,6), 7.28 (d, J = 8 Hz,
2 H, tosyl H-3,5), 5.16 (s, 2 H, ArCH2N), 4.19 (t, J = 5 Hz, 1 H,
CHCH2), 3.25 (d, J = 5 Hz, 2 H, CHCH2), 3.00 (s, 6 H, 2 OCH3),
2.40 (s, 3 H, tosyl CH3).
MS (EI): m/z (%) = 336 (3, [M – 2 OCH2CH3 – H]+), 272, 141, 104,
103 (100), 75.
MS (EI): m/z (%) = 473 (5, [M]+), 318, 216, 215, 76, 75 (100).
Anal. Calcd for C24H29NO4S: C, 67.42; H, 6.84; N, 3.27. Found: C,
67.43; H, 7.03; N, 3.46.
Anal. Calcd for C28H27NO4S: C, 71.01; H, 5.75; N, 2.96. Found: C,
71.07; H, 5.91; N, 3.19.
N-(2,2-Dimethoxyethyl)-N-(2-naphthylmethyl)toluenesulfon-
amide (13)
Fine white needles (EtOAc–Et2O, 1:1); yield from aldehyde: 71%;
N-(2,2-Dimethoxyethyl)-N-(3-phenanthrylmethyl)toluene-
sulfonamide (21)
mp 80–81 °C.
Phenanthrene-3-carbaldehyde reacted with 2,2-dimethoxyethanal
as in the general procedure above, but using benzene (HAZARD)
instead of toluene as the azeotropic solvent. The resulting imine (5
g, 0.017 mol) was reduced by stirring gently for 2 h in AR EtOH
(100 mL) under reflux with NaBH4 (0.97 g, 0.026 mol). Removal of
the solvent produced an oily solid which was extracted with Et2O
(100 mL) and the residue (3.21 g) was filtered off. The extract was
washed with NaOH soln (0.5 M, 150 mL), H2O (100 mL), and dried
(Na2SO4). The Et2O was evaporated to leave 2,2-dimethoxy-N-(3-
phenanthrylmethyl)ethanamine; pale yellow oil; yield: 4.13 g
(82%).
1H NMR (CDCl3): d = 7.80 (dd, J = 6, 3 Hz, 1 H, H-8), 7.76 (super-
imposed d, J = 8 Hz, 1 H and d, J = 8 Hz, 2 H, H-4 and tosyl H-2,6),
7.71 (dd, J = 6, 3 Hz, 1 H, H-5), 7.57 (br s, 1 H, H-1), 7.45 (m, 2 H,
H-6 and H-7), 7.34 (dd, J = 8, 0.7 Hz, 1 H, H-3), 7.30 (d, J = 8 Hz,
2 H, tosyl H-3,5), 4.64 (s, 2 H, ArCH2N), 4.38 (t, J = 5 Hz, 1 H,
CHCH2), 3.26 (d, J = 5 Hz, 2 H, CHCH2), 3.22 (s, 6 H, 2 OCH3),
2.44 (s, 3 H, tosyl CH3).
MS (EI): m/z (%) = 336 (2, [M – 2 OCH3 – H]+), 244, 141, 115, 76,
75 (100).
1H NMR (CDCl3): d = 8.71 (d, J = 8 Hz, 1 H, H-5), 8.62 (s, 1 H, H-
4), 7.88 and 7.85 (2 d, each J = 8 Hz, each 1 H, H-1 and H-8), 7.72
(app s, 2 H, H-9 and H-10), 7.68–7.56 (m, 3 H, H-2,6,7), 4.55 (t,
J = 5 Hz, 1 H, CHCH2), 4.08 (s, 2 H, ArCH2N), 3.38 (s, 6 H, 2
OCH3), 2.84 (d, J = 5 Hz, 2 H, CHCH2).
Anal. Calcd for C22H25NO4S: C, 66.14; H, 6.31; N, 3.51. Found: C,
66.36; H, 6.53; N, 3.48.
N-(2,2-Diethoxyethyl)-N-(2-naphthylmethyl)toluenesulfon-
amide (14)
White crystals (PE–toluene, 17:3); yield from aldehyde: 39%; mp
58.5–59.5 °C.
MS (EI): m/z (%) = 295 (4, [M]+), 222, 191, 95, 88, 75 (100).
This amine reacted with tosyl chloride according to the general pro-
cedure to give 21.
1H NMR (CDCl3): d = 7.79 (dd, J = 6, 3 Hz, 1 H, H-8), 7.75 (d,
J = 8 Hz, 2 H, tosyl H-2,6), 7.73 (d, J = 7.5 Hz, 1 H, H-4), 7.69 (dd,
J = 6, 3 Hz, 1 H, H-5), 7.54 (br s, 1 H, H-1), 7.45 (m, 2 H, H-6 and
H-7), 7.31 (br d, J = ca. 8 Hz, 1 H, H-3), 7.28 (d, J = 8 Hz, 2 H, tosyl
H-3,5), 4.70 (s, 2 H, ArCH2N), 4.56 (t, J = 5 Hz, 1 H, CHCH2), 3.59
and 3.36 (each dq, J = 9, 7 Hz, each 2 H, 2 OCHaHbCH3), 3.27 (d,
J = 5 Hz, 2 H, CHCH2), 2.44 (s, 3 H, tosyl CH3), 1.12 (t, J = 7 Hz,
6 H, 2 OCH2CH3).
White crystals (EtOAc–PE, 1:1); yield: 66%; mp 130–131 °C.
1H NMR (CDCl3): d = 8.42 (dd, J = 7, 2 Hz, 1 H, H-5), 8.36 (br s,
1 H, H-4), 7.87 (dd, J = 7, 2 Hz, 1 H, H-8), 7.81 (d, J = 8 Hz, 1 H,
H-1), 7.79 (d, J = 8 Hz, 2 H, tosyl H-2,6), 7.68 and 7.72 (AB sys-
tem, J = 9 Hz, 2 H, H-9 and H-10), 7.60 (m, 2 H, H-6 and H-7), 7.46
(dd, J = 8, 2 Hz, 1 H, H-2), 7.30 (d, J = 8 Hz, 2 H, tosyl H-3,5), 4.77
(s, 2 H, ArCH2N), 4.45 (t, J = 5 Hz, 1 H, CHCH2), 3.32 (d, J = 5 Hz,
2 H, CHCH2), 3.25 (s, 6 H, 2 OCH3), 2.40 (s, 3 H, tosyl CH3).
MS (EI): m/z (%) = 336 (2, [M – 2 OCH2CH3 – H]+), 272, 141, 104,
103 (100), 75.
MS (EI): m/z (%) = 449 (2, [M]+), 234, 191, 189, 76, 75 (100).
Synthesis 2007, No. 14, 2157–2163 © Thieme Stuttgart · New York