BS-567 (100 MHz) spectrometers in DMSO-d with TMS internal standard. Melting points were determined on a Kofler block.
6
Elemental analyses of all compounds agreed with those calculated.
Vanillyl Alkanoates (3a-d). A solution of vanillin (0.2 mole) in absolute CH Cl (500 mL) was treated with absolute
2
2
pyridine (0.25 mol) and the appropriate acid chloride (0.2 mol) in small portions while shaking the contents of the flask. The
acid chlorides were prepared by boiling for 6 h a mixture of carboxylic acid (1 mol), SOCl (1.3 mol), and absolute benzene
2
(
500 mL) with subsequent distillation of benzene and the solid (in vacuum for dodecanoyl chloride). The reaction mixture was
boiled for 1 h. CH Cl was removed by heating on a water bath. The solid was dissolved in benzene (500 mL), washed three
2
2
times each with water and aqueous NaHCO (5%), and dried over CaCl . The solvent was distilled. The solid was sublimed
3
2
in vacuum or recrystallized from benzene:hexane (1:1).
20
3
a, C H O , yield 85%, bp 155-156°C (0.5 mm Hg), n
D
1.5068. PMR spectrum (δ, ppm): 0.90 (3H, t, Me), 1.12-
1
4
18
4
1
.90 (6H, m, CH ), 2.58 (2H, m, CH ), 3.88 (3H, s, OMe), 7.13 (d, arom. H), 7.44 (m, arom. H), 9.95 (1H, s, CH).
2 2
20
3
b, C H O , yield 82%, bp 163-164°C (0.5 mm Hg), n
1.5092. PMR spectrum (δ, ppm): 0.96 (3H, t, Me), 1.15-
1
5
20
4
D
1
.88 (8H, m, CH ), 2.51 (2H, m, CH ), 3.86 (3H, s, OMe), 7.12 (d, arom. H), 7.45 (m, arom. H), 9.91 (1H, s, CH).
2
2
20
3
c, C H O , yield 77%, bp 170-171°C (0.5 mm Hg), n
1.5079. PMR spectrum (δ, ppm): 0.92 (3H, t, Me), 1.32
1
6
22
4
D
(
(
(
8H, m, CH ), 1.79 (2H, m, CH ), 2.60 (2H, m, CH ), 3.88 (3H, s, OMe), 7.14 (d, ArH), 7.47 (3H, m, ArH), 9.90 (1H, s, CH).
2
2
2
3
d, C H O , yield 75%, oil. PMR spectrum (δ, ppm): 0.89 (3H, t, Me), 1.30 (18H, m, CH ), 1.75 (2H, m, CH ), 2.59
21 32 4 2 2
2H, m, CH ), 3.87 (3H, s, OMe), 7.16 (d, arom. H), 7.41 (m, arom. H), 9.91 (1H, s, CH).
2
2
-Methoxy-4-(11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-yl)phenylCaproylate(4a). 2-Naphthylamine
2, 0.01 mol) was dissolved in ethanol (50 mL), treated with 3a (0.01 mol) and 1a (0.01 mol), boiled for 2 h, and cooled. The
resulting crystalline precipitate was separated, washed with hot methanol, and recrystallized from benzene to afford 4a, 0.9 g
(
60%), C H NO , mp 250-252°C. PMR spectrum (δ, ppm, J/Hz): 0.9 (3H, t, Me), 1.35 (4H, m, CH ), 1.65 (2H, m, CH ),
30 31 4 2 2
2
.40 (2H, m, COCH ), 1.90, 2.20, 2.60 (m, cycloaliphatic H), 3.69 (3H, s, OMe), 5.88 (1H, s, CH), 6.55 (d, J = 8.0, arom. H),
2
6
.73 (d, J = 8.2, arom. H), 7.13 (s, arom. H), 7.30 (m, arom. H), 7.43 (t, arom. H), 7.75 (m, arom. H), 7.95 (d, J = 7.6, arom.
H), 9.70 (s, NH).
2
-Methoxy-4-(11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-yl)phenyl esters of C6 and C7 aliphatic
carboxylic acids (4b and c) were prepared analogously.
2
-Methoxy-4-(11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-yl)phenyl Enanthate (4b). C H NO , yield
31 33 4
6
0%, mp 230-232°C. PMR spectrum (δ, ppm, J/Hz): 0.90 (3H, t, Me), 1.35 (6H, m, CH ), 1.75 (2H, m, CH ), 2.40 (2H, m,
2 2
COCH ), 1.90, 2.20, 2.58 (m, cycloaliphatic H), 3.72 (3H, s, OMe), 5.90 (1H, s, CH), 6.49 (d, J = 7.8, arom. H), 6.62 (d,
2
J = 8.0, arom. H), 7.08 (s, arom. H), 7.30 (m, arom. H), 7.38 (t, arom. H), 7.68 (d, J = 8.8, arom. H), 7.79 (d, J = 7.0, arom. H),
9
.50 (s, NH).
-Methoxy-4-(11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-yl)phenyl Caprylate (4c). C H NO , yield
2
32
35
4
4
8%, mp 201°C. PMR spectrum (δ, ppm, J/Hz): 0.90 (3H, t, Me), 1.30 (8H, m, CH ), 1.65 (2H, m, CH ), 2.40 (2H, m,
2
2
COCH ), 1.90, 2.20, 2.50 (m, cycloaliphatic H), 3.75 (3H, s, OMe), 5.90 (1H, s, CH), 6.48 (d, J = 8.0, arom. H), 6.65 (d,
2
J = 8.7, arom. H), 7.14 (s, arom. H), 7.30 (m, arom. H), 7.40 (m, arom. H), 7.68 (d, J = 6.8, arom. H), 7.73 (d, J = 7.2,
arom. H), 7.95 (d, J = 7.5, arom. H), 9.48 (s, NH).
4
-(9,9-Dimethyl-11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-yl)-2-methoxyphenyl Caproylate (5a).
C H NO . 2-Naphthylamine (2, 0.01 mol) was dissolved in ethanol (50 mL), treated with the appropriate vanillyl hexanoate
32
35
4
(
3a, 0.01 mol) and dimedone (1b, 0.01 mol), boiled for 4 h, and cooled. The resulting crystalline precipitate was separated,
washed with hot methanol, and recrystallized from benzene to afford 5a, 1.09 g (73%), mp 210°C. PMR spectrum (δ, ppm,
J/Hz): 0.90 (3H, t, Me), 1.35 (4H, m, CH ), 1.75 (2H, m, CH ), 2.40 (2H, m, COCH ), 2.15, 2.30 (m, cycloaliphatic H), 3.74
2
2
2
(
(
3H, s, OMe), 5.87 (1H, s, CH), 0.95 (s, 3H, Me), 1.10 (s, 3H, Me), 6.80 (d, J = 8.4, arom. H), 7.12 (d, J = 8.3, arom H), 7.18
s, arom H), 7.34 (m, arom. H), 7.40 (t, arom. H), 7.60 (d, J = 7.8, arom. H), 7.90 (d, J = 7.9, arom. H), 9.37 (s, NH).
4
-(9,9-Dimethyl-11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-yl)-2-methoxyphenyl esters of C , C , and
6 7
C12 aliphatic acids (5b-d) were prepared analogously.
-Methoxy-4-(11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-yl)phenyl Enanthate (5b). C H NO , yield
2
33
37
4
6
0%, mp 184-186°C. PMR spectrum (δ, ppm, J/Hz): 0.90 (3H, t, Me), 1.35 (6H, m, CH ), 1.65 (2H, m, CH ), 2.40 (2H, m,
2 2
COCH ), 2.15, 2.40 (m, cycloaliphatic H), 3.70 (3H, s, OMe), 5.89 (1H, s, CH), 0.95 (s, 3H, Me), 1.10 (s, 3H, Me), 7.00 (d,
2
J = 7.9, arom. H), 7.14 (d, J = 7.3, arom. H), 7.10 (s, arom. H), 7.35 (m, arom. H), 7.37 (t, arom. H), 7.68 (d, J = 6.7, arom. H),
7
.75 (d, J = 7.4, arom. H), 7.95 (d, J = 6.9, arom. H), 9.37 (s, NH).
81