N,N-bis-(3,4-Dimethoxy-ꢁ-phenylethyl)-o-phthalamide (5a), C H N O . Method B. Prepared from
28 32
2
6
homoveratrylamine (3.17 g, 0.017 mol) and phthalic acid chloride (2 g, 9.8 mmol). Yield 82% (3.53 g), mp 150–152°C, R 0.7,
f
Me CO (system 2).
2
–1
1
IR spectrum (KBr, ꢅ, cm ): 3279 (NH), 2922 (Ar-C), 1711 (N-C=O), 1636 (N-C=O), 1590, 1518 (Ar-H). Í NMR
spectrum (400 ÌHz, ÑDCl , ꢄ, ppm, J/Hz): 2.78 (4H, t, J = 7.2, Hꢂ), 3.57 (4H, q, J = 7.2, Hꢁ), 3.78 (6H, s, OCH ), 3.79 (6H,
3
3
s, OCH ), 6.56 (2H, br.t, J = 7.2, NH), 6.70 (2H, dd, J = 2, 8.5, H-6), 6.72 (2H, d, J = 2, H-2), 6.74 (2H, d, J = 8.5, H-5), 7.37
3
and 7.44 (each 2H, m, system AAꢀBBꢀ, H-2ꢀ, 3ꢀ, 4ꢀ, 5ꢀ).
N,N-bis-(3,4-Dimethoxy-ꢁ-phenylethyl)isophthalamide (5b), C H N O . Method A. Prepared from
28 32
2
6
homoveratrylamine (3.06 g, 0.017 mol) and isophthalic acid (1.5 g, 0.009 mol). Yield 29% (1.2 g), mp 132–134°C (Me CO),
2
R 0.47 (system 3).
f
Method B. Prepared from homoveratrylamine (2.1 g, 0.011 mol) and isophthalic acid chloride (1.2 g, 0.006 mol).
Yield 82% (2.33 g).
–1
1
IR spectrum (KBr, ꢅ, cm ): 3316 (NH), 2938 (Ar-C), 1671, 1634 (N-C=O), 1542, 1516 (Ar-H). Í NMR spectrum
(400 ÌHz, ÑDCl , ꢄ, ppm, J/Hz): 2.82 (4Í, t, J = 7, Íꢂ, ꢂꢀ), 3.64 (4Í, q, J = 7, Íꢁ, ꢁꢀ), 3.78 (6Í, s, ÎÑÍ -3, 3ꢀ), 3.80 (6Í,
3
3
s, ÎÑÍ -4, 4ꢀ), 6.18 (2Í, m, NH), 6.68 (2Í, d, J = 2, Í-2, 2ꢀ), 6.69 (2Í, dd, J = 2, 8, Í-6, 6ꢀ), 6.76 (2Í, d, J = 8, Í-5, 5ꢀ), 7.40
3
(1Í, t, J = 7.7, Í-5ꢀꢀ), 7.75 (2Í, dd, J = 2, 8, Í-6ꢀꢀ, 4ꢀꢀ), 8.01 (1Í, t, J = 2, Í-2ꢀꢀ).
N,N-bis-(3,4-Dimethoxy-ꢁ-phenylethyl)terephthalamide (5c), C H N O . Method B. Prepared from
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2
6
homoveratrylamine (2.5 g, 0.013 mol) and terephthalic acid chloride (1.4 g, 0.007 mol). When the reaction was finished, the
amide was extracted by CHCl . The solvent was removed. The residue was crystallized from Me CO. Yield 81.67% (2.77 g),
3
2
mp 219–222°C (Me CO), R 0.44 (system 3).
2
f
–1
1
IR spectrum (KBr, ꢅ, cm ): 3302 (NH), 2938 (Ar-C), 1629 (N-C=O), 1546, 1519 (Ar-H). Í NMR spectrum
(400 ÌHz, ÑDCl , ꢄ, ppm, J/Hz): 2.82 (4Í, t, J = 6.8, Íꢂ, ꢂꢀ), 3.64 (4Í, q, J = 6.8, Íꢁ, ꢁꢀ), 3.78 (6Í, s, ÎÑÍ ), 3.80 (6Í, s,
3
3
ÎÑÍ ), 6.13 (2Í, t, J = 5.6, NH). 6.68 (2Í, d, J = 2, Í-2, 2ꢀ), 6.69 (2Í, dd, J = 2, 8, Í-6, 6ꢀ), 6.76 (2Í, d, J = 8, Í-5, 5ꢀ), 7.65
3
(4Í, s, Í-2ꢀꢀ, 3ꢀꢀ, 5ꢀꢀ, 6ꢀꢀ).
2,3-Dimethoxy-13-hydroxyisoindoloisoquinoline (6), C H NO . Method 1. Polyphosphoric acid (3 g) was
18 17
4
treated with phthalimide 3 (0.3 g), stirred for 4 h at 100°C [5], poured warm into H O (50 mL), and stirred for 2 h. The
2
precipitate was filtered off, washed with warm H O, and crystallized from CH CN. Yield 50% (0.15 g), mp of phosphate 227–
2
3
230°C, R 0.44 (system 2).
f
Method 2. A mixture of 3 (0.5 g) and POCl (0.016 mol) was refluxed on a water bath for 5–6 h. The course of the
3
reaction was monitored by TLC. The reaction mixture was poured onto ice, made basic with NH OH solution (25%), and
4
extracted with CHCl . The solvent was removed. The residue was dissolved in MeOH (40 mL), cooled to 0–5°C, and treated
3
in portions with NaBH (0.04 mol). The MeOH was distilled off. The residue was dissolved in H O and extracted with
4
2
CHCl . The CHCl was removed. The residue was crystallized from Me CO. Yield 42% (0.21 g), mp 185–188°C, R 0.44
3
3
2
f
(system 2).
–1
1
IR spectrum (KBr, ꢅ, cm ): 3332 (ÎH), 2926 (Ar-C), 1670 (C=O), 1516, 1469, 1453, 1438 (Ar-H). Í NMR
spectrum (400 ÌHz, ÑDCl , ꢄ, ppm, J/Hz): 2.62 (1H, ddd, J = 1.6, 4.3, 16.2, Í-5å), 2.83 (1Í, ddd, J = 16.2, 12.0, 5.9, Í-5à),
3
3.30 (1Í, ddd, J = 13.1, 12.0, 4.3, Í-6à), 3.77 (3Í, s, ÎÑÍ -2), 3.89 (3Í, s, ÎÑÍ -3), 4.03 (1Í, ddd, J = 13.1, 5.9, 1.6, Í-6å),
3
3
4.2 (1Í, s, ÎÍ-13), 6.50 (1Í, s, H-4), 7.35 (1Í, s, Í-1), 7.42 (2Í, dt, J =7.5, 1.2, Í-10), 7.58 (1Í, td, J = 7.8, 1.2, Í-11), 7.64
(1Í, d, J = 7.5, Í-9). 7.93 (1Í, d, J = 7.8, Í-12).
13
Ñ NMR spectrum (100 ÌHz, ÑDCl , 20ꢃC, ꢄ, ppm): 29.25 (Ñ-5), 34.98 (Ñ-6), 56.07 (Ñ-3), 56.31 (Ñ-2), 86.51
3
(Ñ-13), 110.38 (Ñ-4), 111.51 (Ñ-1), 123.14 (Ñ-12), 123.76 (Ñ-9), 127.67 (Ñ-4à), 127.78 (Ñ-1à), 129.66 (Ñ-10), 130.64 (Ñ-8),
132.79 (Ñ-11), 148.06 (Ñ-2), 148.25 (Ñ-12à), 149.42 (Ñ-3), 167.55 (Ñ-7).
2,3-Dimethoxy-5,6-dihydroisoindolyl[1,2-a]isoquinolin-8(12bH)-one (7), C H NO . Imide 3 (0.2 g) was
18 17
3
dissolved in MeOH:CHCl (3:2), treated at room temperature in portions with NaBH (0.8 g), held at room temperature for
3
4
1 h, treated with conc. HCl until acidic, and refluxed on a water bath for 2 h. The course of the reaction was monitored by TLC.
The solvent was distilled off. The residue was dissolved in H O and extracted with CHCl . The CHCl was removed. The
2
3
3
residue was crystallized from Me CO. Yield 100%, mp 173–175°C, R 0.2 (system 2).
2
f
1
Í NMR spectrum (400 ÌHz, ÑDCl , ꢄ, ppm, J/Hz): 2.71 (1Í, dt, J = 4, 7.8. Í-5), 2.95 (1Í, m, Í-5), 3.36 (1Í, m,
3
Í-6à), 3.79 (3Í, s, ÎÑÍ ), 3.87 (3Í, s, ÎÑÍ ), 4.44 (1Í, m, Í-6å), 5.56 (1Í, s, H-13), 6.60 (1Í, s, H-4), 7.10 (1Í, s, Í-1),
3
3
7.43* (1Í, t, J = 7.3, Í-10), 7.55* (1Í, td, J = 1, 7.5, Í-11), 7.77** (1Í, d, J = 7.6, Í-9), 7.82** (1Í, d, J = 7.6, Í-12).
1102