ORDER
REPRINTS
DIMETHYLACETAL CYCLIZATION
405
NaOHaq. at 0◦C, then extracted with CHCl3 (50 mL × 2). The combined extract
was dried over anhydrous Na2SO4 and concentrated in vacuo to give 1-benzyl-3-
[(3,4-dimethoxyphenethyl)amino]piperidine 6 (14.2 g, 90%) as a yellow oil. To a
solution of 6 (14.2 g, 40.1 mmol) and Et3N (6.70 mol, 48.1 mmol) in THF (100 mL)
was added dropwise a solution of methyl chloroformate (3.40 mL, 44.1 mmol) in
THF (10 mL) at 0◦C, and the mixture was stirred at 0◦C for 1 h. The result-
ing mixture was concentrated in vacuo and the residue was dissolved in H2O
(150 mL), then extracted with AcOEt (50 mL × 2). The combined extract was
washed with 1 N NaOHaq. (100 mL), dried over anhydrous Na2SO4, and concen-
trated in vacuo to give 2 (16.2 g, 98%) as a yellow oil. This material may be used
in the next cyclization step or converted to its oxalate salt. The oxalate salt was
obtained from MeOH–AcOEt as a colorless powder: m.p. 145–146◦C; 1H NMR
(400 MHz, DMSO-d6) δ 1.68–1.78 (4H, m, 4-H2 and 5-H2 of piperidine), 2.41 (2H,
br s, 1-H2 or 6-H2 of piperidine), 2.66 (2H, br s , 3,4-(OMe)2PhCH2), 2.95–2.97
(2H, m, 1-H2 or 6-H2 of piperidine), 3.27–3.29 (2H, m, MeO2 CNCH2), 3.60 (3H,
s, OMe), 3.72 (3H, s, OMe), 3.74 (3H, s, OMe), 3.95 (3H, br s, CH2Ph and 3-H of
piperidine), 6.70 (1H, d, J = 7.2 Hz, 5- or 6-H of 3,4-(OMe)2Ph), 6.78 (1H, s, 2-H
of 3,4-(MeO)2Ph), 6.86 (1H, d, J = 7.2 Hz, 5- or 6-H of 3,4-(MeO)2Ph), 7.40 (5H,
brs, CH2Ph); MS (FAB) m/z 413 (MH+); Anal. calcd. for C24H32N2O4 · C2H2O4:
C 62.14, H 6.82, N 5.57. Found: C 62.01, H 6.81, N 5.47.
(
)-2-(1-Benzyl-3-piperidyl)-6,7-dimethoxy-1-oxo-1,2,3,4-tetrahydroi-
soquinoline(7)and( )-6,7-dimethoxy-1-oxo-2-[1-(trifluoromethanesulfonyl)-
3-piperidyl]-1,2,3,4-tetrahydroisoquinoline (8). To a solution of 2 (6.31 g,
15.3 mmol) and DMAP (4.67 g, 38.2 mmol) in CH2Cl2 (120 mL) was added drop-
wise a solution of Tf2O (10.3 mL, 61.2 mmol) in CH2Cl2 (10 mL) at 0◦C, and
the mixture was stirred at room temperature for 3 days. The reaction mixture was
partitioned between CHCl3 (50 mL × 2) and H2O (150 mL) and the combined
CHCl3 layer was dried over anhydrous Na2SO4 and concentrated in vacuo to give
a mixture of 7 and 8. The mixture can be separated by column chromatography
on silica gel (CHCl3/MeOH = 49/1 for 7, 99/1 for 8) to give 7 (3.11 g, 53%) as a
yellow oil and 8 as a yellow form.
Compound 7 may be converted to its hydrochloride salt. The hydrochloride
salt of 7 was obtained from EtOH–AcOEt as a colorless powder: m.p. 232–238◦C;
1H NMR (400 MHz, DMSO-d6) δ 1.74–1.93 (4H, m, 4-H2 and 5-H2 of piperidine),
2.87 (2H, br s, 4-H2 of isoquinoline), 2.88 (1H, br s, 1-H or 6-H of piperidine),
3.19–3.24 (2H, m, 1-H and 6-H of piperidine), 3.31 (1H, br s, 1-H or 6-H of
piperidine), 3.44 (2H, br s, 3-H2 of isoquinoline), 3.75 (3H, s, OMe), 3.81 (3H, s,
OMe), 4.32 (2H, t, J = 4.8 Hz, CH2Ph), 4.85–4.87 (1H, m, 3-H of piperidine),
6.89 (1H, s, 5-H of isoquinoline), 7.34 (1H, s, 8-H of isoquinoline), 7.46–7.48 (3H,
m, CH2Ph), 7.59–7.61 (2H, m, CH2Ph), 10.64 (1H, brs, HCl); MS (FAB) m/z 381
(MH+); Anal. calcd. for C23H28N2O3 · HCl · 0.3H2O: C 65.41, H 7.06, N 6.63, Cl
8.39. Found: C 65.38, H 7.12, N 6.65, Cl 8.17.