Synthesis of 5-aryl-1,2,3,4-tetrahydrobenzo[a]phenanthridines

Article abstract of DOI:10.1023/A:1012355506689

Previously unknown derivatives of tetrahydro[a]phenanthridine containing annelated benzoquinoline and cyclohexene nuclei were prepared by condensation of azomethines of the 2-naphthylamine series with cyclohexanone. The possibility of synthesis of such compounds without preliminarily preparing Schiff bases was demonstrated. The effect of substituents in the aromatic ring of the azomethine on the yield of the target products was elucidated. The IR, UV, ¹H NMR, and mass spectra of the synthesized compounds were discussed.

Full text of DOI:10.1023/A:1012355506689

Russian Journal of General Chemistry, Vol. 71, No. 2, 2001, pp. 250 256. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 2, 2001,
pp. 279 285.
Original Russian Text Copyright
2001 by Kozlov, Basalaeva.
Synthesis of 5-Aryl-1,2,3,4-tetrahydrobenzo[a]phenanthridines
N. G. Kozlov and L. I. Basalaeva
Institute of Physical Organic Chemistry, Academy of Sciences of Belarus, Minsk, Belarus
Received September 14, 1999
Abstract Previously unknown derivatives of tetrahydro[a]phenanthridine containing annelated benzoquino-
line and cyclohexene nuclei were prepared by condensation of azomethines of the 2-naphthylamine series
with cyclohexanone. The possibility of synthesis of such compounds without preliminarily preparing Schiff
bases was demonstrated. The effect of substituents in the aromatic ring of the azomethine on the yield of the
1
target products was elucidated. The IR, UV, H NMR, and mass spectra of the synthesized compounds were
discussed.
Quinoline derivatives, while being a well-do-
cumented class of compounds, are attracting ever
increasing attention. This is explained by the prepara-
tion on the basis of natural and synthetic quinoline
bases of antitumor [1, 2] and antomicrobial agents [3,
4]. Moreover, these compounds are structural analogs
of alkaloids [5], enzyme inhibitors [6], and antibiotics
[7, 8].
synthesis of 5-aryl-1,2,3,4-tetrahydrobenzo[a]phe-
nanthridine by reaction of azomethines of the 2-
naphthylamine series with cyclohexanone or by reac-
tion of 2-naphthylamine, an aldehyde, and cyclohexa-
none. Azomethines IVa IVu were prepared by reac-
tions of 2-naphthylamine (I) with benzaldehydes
IIIa IIIu in alcoholic solution under heating for 10
20 min. The yields, melting points, and elemental
analyses of the products are listed in Table 1.
Of particular interest among quinoline bases are
derivatives of 5,6-benzoquinoline whose nucleus is a
structural unit of lysergic acid and its physiologically
active analogs [9, 10]. The presence of alternating
benzene rings and heterorings makes possible varying
physicochemical properties of the molecule, thus
varying its physiological activity.
The IR spectra of azomethines IVa IVu display a
characteristic band of N=CH stretching vibrations in
1
the range 1632 1605 cm . The spectra of IVe, IVj,
1
and IVn show strong bands at 1535 and 1370 cm
[ (NO2)], and the spectra of IVh, IVq, and IVs, a
broad band of hydroxyl stretching vibrations at 3450
1
3430 cm . Stretching vibrations of the C F bond in
The aim of the present work was to develop syn-
thetic procedures for 5-aryl-1,2,3,4-tetrahydrobenzo-
[a]phenanthridines incorporating both benzoquinoline
and cyclohexene nuclei.
1
IVb appear at 1150 cm , of the C Br bond in IVd,
1
IVm, and IVs, at 670 520 cm (a medium band),
1
and of the C Cl bond in IVc, at 830 cm .
Compounds IVa IVu are fairly stable to electron
impact. The base peak in the mass spectra of most
azomethines is a molecular ion peak (M+). The most
important fragmentation pathways of the molecular
As shown in [11], phenylmethylene-2-naphthyl-
amine and its derivatives react with cyclohexanone,
yielding 5,6-benzoquinoline derivatives. The con-
densation was performed in the presence of nitro-
benzene under pressure (in ampule) at 140 145 C.
The reaction under mild conditions (without heating,
in the presence of a small amount of catalyst) gave a
mixture of the corresponding -arylaminoketone
[(aryl)(2-naphthylamino)methyl]cyclohexanone, and a
cyclization product, a hydroxy derivative of tetra-
hydrobenzoquinoline, 2-aryl-3,4-(1,2-cyclohexahexa-
nediyl)-4-hydroxy-1,2,3,4-tetrahydro-5,6-benzoquino-
line. -Arylaminoketones are also considered as
intermediate products in the Baeyer synthesis of
quinoline bases [12].
ion involve generation of an [M
1]+ ion and of
[M HCN]+ or [(M 1) HCN]+ ions (weak peaks).
Tetrahydrobenzo[a]phenanthridines VI were syn-
thesized refluxing a solution of an azomethine and
cyclohexanone (1:3) in ethanol for 1 6 h in the
presence of catalytic amounts of HCl. In the absence
of catalyst the reaction almost fails: Either the starting
materials are recovered or strong tarring of the reac-
tion mixture occurs. Sometimes the reaction was per-
formed without preliminarily preparing azomethines.
In these cases, equimolar amounts of 2-naphthylamine
and a substituted benzaldehyde IIIv III was ref-
In the present work we accomplished a selective
1070-3632/01/7102-0250$25.00 2001 MAIK Nauka/Interperiodica

SYNTHESIS OF 5-ARYL-1,2,3,4-TETRAHYDROBENZO[a]PHENANTHRIDINES
251
Table 1. Yields, melting points, and elemntal analyses of arylmethylene-2-naphthylamine IVa IVu
Found, %
Calculated, %
Comp. Yield,
%
mp,
C
Formula
C
H
N (Hlg)
C
H
N (Hlg)
IVa
IVb
IVc
IVd
IVe
IVf
IVg
IVh
IVi
95
90
90
90
90
84
80
70
65
60
57
50
53
60
40
40
40
45
38
35
45
97
110
119
128
122
88.34
5.60
6.08
5.65
C17H13N
C17H12FN
88.31
81.92
76.98
65.80
73.91
88.03
83.08
82.59
85.45
73.91
88.16
83.08
65.80
73.91
85.45
78.35
77.57
77.57
62.58
81.52
78.54
5.63
4.82
4.52
3.87
4.35
6.56
5.75
5.26
5.64
4.35
6.12
5.75
3.87
4.35
5.26
5.84
4.94
4.94
3.68
5.98
4.72
6.06
5.62 (7.63)
5.28 (13.22)
4.52 (25.81)
76.99
65.76
73.88
88.00
83.08
82.61
85.43
73.89
88.13
83.04
65.83
73.89
85.48
78.31
77.52
77.59
62.60
81.54
78.52
4.52
3.89
5.26 (13.24) C17H12ClN
4.50 (25.81) C17H12BrN
C17H12N2O2
4.37
6.59
5.73
5.23
5.66
4.38
6.10
5.76
3.89
4.37
5.28
5.82
4.90
4.92
3.67
5.99
4.74
10.15
10.14
79 80
99 100
228 230
145
94
87 88
60
102 103
100
59
131 132
182
5.40
5.37
5.64
4.17
10.11
5.70
5.38
C19H17N
5.41
5.36
5.67
4.15
10.14
5.72
5.36
C18H15NO
C17H13NO
C24H19NO
C17H12N2O2
C18H15N
IVj
IVk
IVl
C18H15NO
IVm
IVn
IVo
IVp
IVq
IVr
IVs
IVt
4.54 (25.80) C17H12BrN
10.16
4.31
4.79
5.35
5.30
4.27 (24.55) C17H12BrNO
3.79
5.11
4.52 (25.81)
C17H12N2O2
C23H17NO
C19H17NO2
C17H13NO2
C17H13NO2
10.14
4.33
4.81
5.32
5.32
4.29 (24.53)
3.80
5.09
172
162
108 109
122
C25H22NO2
C18H13NO2
IVu
luxed in ethanol solution for 1 2 h, and, after cooling,
not isolating the resulting Schiff base (most com-
monly, a viscous liquid), a triple excess of cyclo-
hexanone (with respect to the Schiff base) and a
catalytic amount of HCl were added. Refluxing was
continued for an additional 1.5 6 h. The reaction
products were mostly isolated as crystals.
cleavage under the action of HCl to give 2-naphthyl-
amine and 2-(3,4-dimethoxyphenylmetylene)cyclo-
hexanone, whereas tetrahydrobenzo[a]phenanthridines
are stable and undergo no chemical transformations
upon prolonged refluxing in HCl.
The reaction occurs by Scheme 1.
The reaction is made possible by the mobility of
the hydrogen atom to the carbonyl group of cyclo-
hexanone. In the presence of acid catalyst, the nucleo-
philic substitution of cyclohexanone occurs in such a
Based on published data [11 13], we suggest
intermediate formation of arylaminoketones and tetra-
hydrobenzoquinolines. However, arylaminoketone
could be isolated only in the case of 5-(3,4-dimethoxy- way that its mobile hydrogen atom adds at the nitro-
phenyl)-1,2,3,4-tetrahydrobenzo[a]phenanthridine
(VIo). 2-[(4,5-Dimethoxyphenyl)(2-naphthylamino)-
methyl]cyclohexanone (V) (mp 197 C) formed after
10-min refluxing in ethanol of (3,4-dimethoxyphenyl)-
methylene-2-naphthylamine (IVo) and a triple excess
gen atom and the rest molecule, at the carbon atom of
the azomethine bond, resulting in arylaminoketone
formation. The arylaminoketone undergoes cyclization
followed by dehydration to give the final product,
5-aryl-1,2,3,4-tetrahydrobenzo[a]phenanthridine VIa
of cyclohexanone in the presence of a catalytic VI . As the catalyst we used concentrated hydro-
amount of HCl. The IR spectrum revealed in the
chloric acid whose role is to activate the ketone
molecule and to polarize the azomethine bond. The
electronic nature of substituents in the azomethine
molecule has a considerable effect on the polarization
and activity of the azomethine bond. Acceptor sub-
stituents in the para position of the aldehyde part of
the azomethine, via conjugation of the benzene ring
and the azomethine bond increase the positive charge
1
product a secondary amino group (3240 cm ) and a
1
CO group (1574 cm ). The reduced intensities of the
amino and carbonyl absorption bands are apparently
explained by intramolecular H bonding, which agrees
with published data [14]. Moreover, 2-[(4,5-di-
methoxyphenyl)(2-naphthylamino)methyl]cyclo-
hexanone (V) is readily available for hydramine
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 2 2001

252
KOZLOV, BASALAEVA
Scheme 1.
R
3
2
4
5
5
3
6
2
6
O
R
4
NH2
N
1
+
IVa IV
IIIa III
I
O
II
R
R
3
3
2
1
4
7
2
4
5
5
1
6
12
11
O
N
NH
10
9
8
VIa VI
V
R = H (IIIa, IVa, VIa), 4 -F (IIIb, IVb, VIb), 4 -Cl (IIIc, IVc, VIc), 4 -Br (IIId, IVd, VId), 4 -NO2 (IIIe, IVe, VIe),
4 -CH2CH3 (IIIf, IVf, VIf), 4 -OCH3 (IIIg, IVg, VIg), 4 -OH (IIIh, IVh, VIh), 4 -OCH2C6H5 (IIIi, IVi, VIi), 2 -NO2
(IIIj, IVj, VIj), 2 -CH3 (IIIk, IVk, VIk), 2 -OCH3 (IIIl, IVl, VIl), 3 -Br (IIIm, IVm, VIm), 3 -NO2 (IIIn, IVn, VIn),
3 -OC6H5 (IIIo, IVo, VIo), 3 ,4 -di-OCH3 (IIIp, IVp, V, VIp), 2 ,4 -di-OH (IIIq, IVq, VIq), 3 ,4 -di-OH (IIIr, IVr, VIr),
5 -Br-2 -OH (IIIs, IVs, VIs), 4 -OCH2C6H5-3 -OCH3 (IIIt, IVt, VIt), 3 ,4 -OCH2O (IIIu, IVu, VIu), 2 -CF3 (IIIv, IVv,
VIv), 3 -OH (IIIw, IVw, VIw), 2 ,3 -di-OCH3 (IIIx, IVx, VIx), 2 ,5 -di-OCH3 (IIIy, IVy, VIy), 4 -OH-3 -OCH2CH3
(IIIz, IVz, VIz), 3 -OCH2C6H5-4 -OH (III , IV , VI ).
on the azomethine carbon atom and facilitates addition
of the anion of cyclohexanone. Here, therefore, the
high-melting white or light yellow crystals. Their
physicochemical characteristics are listed in Table 2.
yield is markedly higher than with electron-donor Compounds VIc VIe, and VIn have been described
substituents.
in [11].
It can be proposed that ortho-substituents produce
a steric effect on the reaction center of the azomethine
group. An ortho-nitro substituent sightly reduces the
yield of the target product, regardless of the fact that
the electronic effect of this group favors the reaction.
A stronger steric effect is observed in o-methyl (IVk),
o-methoxy (IVl), and o-trifluoromethyl (IVv) deriva-
tives of phenylmethylene-2-naphthylamines.
The absence in the IR spectra of compounds VIa
VIf (Table 3) of bands in the range 1725 1650 cm ,
1
characteristic of carbonyl stretching vibrations, as well
1
as of bands in the range 3400 3300 cm , character-
istic of amino group, suggests that one deals here with
a cyclic tertiary amine. Methylene groups of the cyclo-
1
hexene ring give two bands at 2920 2880 cm , and
the bands of stretching vibrations of aromatic CH
1
bonds are at 3065 3050 cm . A strong band in the
Disubstituted azomethines require more severe
conditions to convert into a phenanthridine derivative.
Thus, the reactions with 5-bromo-2-hydroxy- and 2,5-
dimethoxy-substituted azomethines IVs, IVy were
performed for 6 h at increased concentration of the
catalyst. The yields of the target products were no
higher than 13%.
1
region of 2860 cm (OCH3) is present in the spectra
of VIg, VIl, VIo, VIt, VIx, and VIy. Compounds VIe,
1
VIj, and VIn give bands at 1365 and 1530 cm ,
related respectively to symmetric and antisymmetric
vibrations of the N O bond.
The UV spectra of tetrahydrobenzo[a]phenanthri-
dines VIa VI (Table 4) are typical of azophenan-
Tetrahydrobenzo[a]phenanthridines VIa VI are
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 2 2001

SYNTHESIS OF 5-ARYL-1,2,3,4-TETRAHYDROBENZO[a]PHENANTHRIDINES
253
Table 2. Yields, melting points, and elemental analyses of 5-aryl-1,2,3,4-tetrahydrobenzo[a]phenanthridines VIa VI
Found, %
Calculated, %
H N (Hlg)
Comp. Yield,
mp,
C
Formula
no.
%
C
H
N (Hlg)
C
VIa
VIb
VIc
VId
VIe
VIf
VIg
VIh
VIi
80
85
80
80
74
55
42
40
35
66
46
44
63
74
40
50
20
46
13
18
20
45
50
20
10
54
50
122 124
258 260
200 202
220
89.31
6.17
4.52
4.30
C23H19N
C23H18FN
89.32
84.40
80.47
71.13
77.97
89.02
84.96
84.92
86.75
77.97
89.16
84.96
71.13
77.97
79.30
82.30
80.94
80.94
68.31
83.60
81.59
76.39
84.92
82.30
82.30
82.30
83.52
6.15
5.50
5.25
4.65
5.08
6.83
6.19
5.85
6.02
5.08
6.50
6.19
4.65
5.08
5.74
6.23
5.57
5.57
4.45
6.07
5.38
4.77
5.85
6.23
6.23
6.23
5.80
4.53
4.28
4.05 (10.23)
3.60 (20.62)
7.91
4.15
4.13
4.31
3.37
7.91
4.34
4.13
3.60 (20.62)
7.91
3.50
3.80
4.11
4.11
3.46
3.15
3.97
3.71
4.31
3.80
3.80
3.80
80.45
71.13
77.95
89.00
84.93
84.90
86.73
78.00
89.13
84.96
71.10
77.98
79.27
82.33
80.90
80.92
68.28
83.57
81.57
5.22
4.61
5.13
6.84
6.20
5.87
6.00
5.04
6.50
6.20
4.61
5.06
5.72
6.21
5.56
5.55
4.47
6.04
5.35
4.06 (10.20) C23H18ClN
3.62 (20.58) C23H18BrN
240 242
198 199
182 183
292 294
149 150
238 239
175 176
224 226
248 250
226 230
254
214 216
224
294 296
271
192 193
251 252
101 102
268
7.88
4.13
4.17
4.29
3.40
7.90
4.33
4.15
C23H18N2O2
C25H23N
C24H21NO
C23H19NO
C30H25NO
C23H18N2O2
C24H21N
VIj
VIk
VIl
C24H21NO
VIm
VIn
VIo
VIp
VIq
VIr
VIs
VIt
VIu
VIv
VIw
VIx
VIy
VIz
VI
3.63 (20.59) C23H18BrN
7.95
3.51
3.78
4.11
4.13
3.48
3.20
3.94
3.70
4.28
3.76
3.80
3.80
3.23
C23H18N2O2
C29H23NO
C25H23NO2
C23H19NO2
C23H19NO2
C23H18BrNO
C31H27NO2
C24H19NO2
C24H18F3N
C23H19NO
C25H23NO2
C25H23NO2
C25H23NO2
C30H25NO2
84.90
82.32
82.31
82.29
83.54
5.87
6.25
6.23
6.20
5.82
157
145
237 238
260 261
3.25
threne structures. The condensation of the benzoquino-
line nucleus with an alicycle produces a bathochromic
shift of absorption maxima and increase in their
intensity compared with unsubstituted benzoquinoline,
which has also been noted in [15].
internal reference TMS. The mass spectra were re-
corded on an MX-1320 instrument. The UV spectra
were taken on a Specord UV-Vis spectrophotometer
4
for 1 10 M ethanol solutions.
5-Aryl-1,2,3,4-tetrahydrobenzo[a]phenanthri-
dines VIa VI . Method I (for VIa VIu). a. Aldehyde
IIIa IIIu, 0.1 mol, and 0.1 mol of 2-naphthylamine
(I) in 50 ml of benzene was heated under reflux with
a Dean Stark trap for 1 2 h. The solvent was then
removed by distillation, and the residue was recrystal-
lized from ethanol to obtain arylmethylene-2-naphthyl-
amine IVa IVu (Table 1).
The long-wave band has vibrational structure.
When there is an electron-acceptor substituent in the
para position of the benzene ring (compounds VIc
VIe), the long-wave maxima smoothen and suffer a
bathochromic shift, except for compound VIb, the
fluorine substituent in which produces a hypsochro-
mic shift [16].
EXERIMENTAL
b. Cyclohexanone (II), 0.03 mol, and 5 6 drops of
conc. HCl acid were added to a solution of 0.01 mol
of Schiff base IVa IVu in 50 ml of ethanol, and the
mixture was heated under reflux for 1 6 h, depending
on substitution pattern in the benzene ring of aryl-
methylene-2-naphthylamine. The crystals that formed
The IR spectra were measured on a UR-20 spec-
1
trophotometer in KBr. The H NMR spectra were
obtained on Bruker AC-300 (300 MHz) or Tesla BS-
567 (100 MHz) for 2 5% solutions in DMSO-d6,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 2 2001

254
KOZLOV, BASALAEVA
Table 3. 1H NMR and mass spectra of 5-aryl-1,2,3,4-tetrahydrobenzo[a]phenanthridines VIa VI
1H NMR spectrum, , ppm (J, Hz)
Comp.
no.
4H
Mass spectrum, m/z (Irel, %)
C1 H2 (C2 H2, C4 H2
C3 H2)
aromatic protons and protons in R
VIa
VIb
3.60 m 1.80 m 2.85 m 7.59 8.20 m, 8.60 8.80 m
3.65 m 1.85 m 2.90 m 7.39 7.50 m, 7.65 7.83 m, 7.87 s, 8.02 8.21 m, 328 (20), 327 (92), 326 (100),
8.82 8.90 m 298 (10), 251 (21), 109 (23)
VIca 3.80 m 1.78 m 2.78 m 7.01 d (8.0), 7.30 d (7.0), 7.56 m, 7.60 7.79 m, 344 (10), 343 (80), 342 (100),
7.85 m, 7.98 8.20 m, 8.78 8.92 m 232 (15), 111 (10)
3.59 m 1.81 m 2.82 m 7.45 7.58 m, 7.64 7.80 m, 7.90 8.12 m, 8.23 389 (15), 388 (95), 387 (100),
309 (100), 233 (52), 232 (20)
VId
8.90 m
232 (13), 156 (20)
VIea 3.52 m 1.82 m 2.82 m 7.68 7.89 m, 7.99 8.11 m, 8.30 8.50 m, 8.80 354 (100), 308 (43), 277 (30)
8.85 m
VIfa 3.80 m 1.90 m 2.50 m 7.48 d (5.8), 7.52 d (6.0), 7.81 7.89 m, 8.00 8.20 m, 337 (100), 322 (80), 308 (30),
8.55 8.80 m, 9.40 d (6.2), 1.35 m (3H, CH2CH3), 260 (20)
2.55 q (2H, CH2CH3)
VIg
3.58 m 1.79 m 2.82 m 7.00 m, 7.08 m, 7.45 m, 7.54 m, 7.60 7.80 m, 340 (52), 339 (100), 308 (70),
7.85 m, 7.92 8.12 m, 8.70 8.89 m, 3.82 s (3H, OCH3) 262 (25)
VIha 3.52 m 1.75 m 2.85 m 6.88 6.94 m, 7.77 7.43 m, 7.63 7.70 m, 7.81 d (7.3), 326 (15), 325 (63), 324 (100),
7.60 d (8.0), 8.00 8.08 m, 9.50 s (1H, OH)
308 (15), 248 (20), 155 (12),
139 (28)
VIi
3.60 m 1.70 m 3.10 m 6.90 7.20 m, 7.30 7.60 m, 7.63 7.80 m, 7.83 416 (20), 415 (80), 337 (40),
8.10 m, 8.70 8.90 m, 5.19 s (2H, OCH2)
3.60 m 1.70 m 2.70 m 7.55 8.28 m, 8.70 8.92 m
338 (100), 322 (50), 308 (42)
354 (100), 308 (50), 276 (37)
VIj
VIk
3.60 m 1.80 m 3.16 m 7.20 7.40 m, 7.60 7.80 m, 7.85 m, 7.92 8.15 m, 324 (30), 323 (100), 308 (25)
8.75 8.93 m, 2.00 s (3H, CH3)
VIl
3.55 m 1.75 m 3.10 m 7.10 7.40 m, 7.50 7.90 m, 8.70 8.90 m, 3.80 s 340 (25), 339 (100), 338 (92),
(3H, OCH3)
308 (75), 234 (33), 152 (34),
139 (50), 40 (35), 36 (62)
VIm 3.60 m 1.60 m 2.80 m 7.42 7.80 m, 7.85 7.90 m, 7.97 8.12 m, 8.72 389 (20), 388 (90), 387 (100),
8.90 m 232 (10), 156 (15)
3.65 m 1.75 m 2.80 m 7.62 7.95 m, 8.00 8.19 m, 8.25 8.49 m, 8.70 355 (20), 354 (100), 308 (30),
VIn
VIo
8.90 m
276 (25)
402 (70), 401 (100), 324 (20),
308 (15)
3.55 m 1.80 m 2.80 m 7.00 8.05 m, 8.70 8.90 m
VIpa 3.59 m 1.83 m 2.89 m 7.02 7.13 m, 7.15 s, 7.62 7.75 m, 7.85 d (9.2), 369 (100), 354 (30), 339 (45),
8.00 d (9.0), 8.05 8.12 m, 8.82 d (7.3), 3.8 s (3H, 307 (20), 292 (13)
OCH3), 3.88 s (3H, OCH3)
VIq
VIr
VIs
3.50 m 1.60 m 2.85 m 6.80 7.00 m, 7.60 8.10 m, 8.70 8.85 m, 9.06 br.s 341 (60), 340 (100), 307 (13),
(2OH) 264 (18), 139 (13)
3.55 m 1.75 m 2.80 m 6.90 7.55 m, 7.80 8.12 m, 8.8 m, 9.05 br.s (2OH) 341 (66), 340 (100), 307 (13),
264 (18), 139 (20)
3.40 m 1.80 m 2.72 m 6.90 7.05 m, 7.30 7.50 m, 7.60 7.80 m, 7.82 405 (20), 404 (95), 405 (100),
7.90 m, 7.95 8.15 m, 8.72 8.90 m, 10.01 br.s 387 (10), 324 (15), 307 (30),
(1H, OH)
80 (25)
VIt
3.60 m 1.85 m 2.88 m 6.88 s, 7.10 s, 7.20 7.70 m, 7.84 7.95 m, 8.70 446 (80), 445 (100), 430 (27),
8.84 m, 5.22 s (2H, OCH2), 3.93 s (3H, OCH3) 414 (18), 369 (53), 338 (32)
VIu
3.59 m 1.80 m 2.85 m 7.10 s, 7.15 d (7.4), 7.70 7.82 m, 7.90 s, 8.00 8.20 m 353 (10), 352 (15), 272 (50),
8.80 8.99 m, 6.20 s (2H, OCH2O)
143 (12), 135 (100), 77 (10)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 2 2001

SYNTHESIS OF 5-ARYL-1,2,3,4-TETRAHYDROBENZO[a]PHENANTHRIDINES
Table 3. (Contd.)
255
1H NMR spectrum, , ppm (J, Hz)
Comp.
no.
4H
Mass spectrum, m/z (Irel, %)
C1 H2 (C2 H2, C4 H2
C3 H2)
aromatic protons and protons in R
VIva 3.60 m 1.80 m 2.50 m 7.50 d (7.3), 7.62 7.80 m, 7.88 d (9.0), 7.94 8.15 m 378 (10), 377 (100), 376 (80),
8.73 8.92 m
308 (20), 232 (30), 145 (40)
326 (10), 325 (80), 324 (100),
308 (20), 248 (18), 155 (9),
139 (30)
VIw 3.55 m 1.79 m 2.80 m 6.80 7.00 m, 7.20 7.40 m, 7.60 7.90 m, 7.93
8.19 m, 8.70 8.84 m, 9.60 s (1H, OH)
VIxa 3.53 m 1.90 m 2.50
2.60 m, 7.80 8.01 m, 8.80 8.90 m, 3.52 s (3H, OCH3), 3.90 s 292 (30)
6.61 d (7.5), 6.90 d (9.6), 7.30 d (9.0), 7.53 7.60 m, 369 (100), 354 (25), 339 (40),
2.85
(3H, OCH3)
3.00 m
VIya 3.60 m 1.80 m 2.50
6.75 d (7.5), 6.83 7.00 m, 7.52 7.60 m, 7.75 d (6.6), 326 (30), 325 (85), 324 (100),
2.80 m 7.84 d (7.0), 7.85 8.00 m, 8.73 8.77 m, 3.62 s (3H, 308 (15), 248 (20), 155 (15),
2.84
OCH3), 3.75 s (3H, OCH3)
139 (40)
2.95 m
VIz
VI
3.56 m 1.70 m 2.90 m 7.0 s, 7.20 d (8.3), 7.60 7.85 m, 7.90 8.22 m, 8.70 369 (100), 352 (70), 334 (20),
8.90 m, 1.33 m (3H, OCH2CH3), 4.09 q (2H, OCH2 317 (15)
CH3),
3.50 m 1.75 m 2.50 m 6.88 7.70 m, 7.90 8.20 m, 8.80 8.90 m, 9.20 431 (100), 414 (20), 337 (15),
(1H, OH), 5.19 s (2H, OCH2) 324 (10), 308 (25)
9.60 s (1H, OH)
a
1
The H NMR spectra were obtained on a Bruker AC-300 spectrometer (300 MHz).
Table 4. UV spectra 5-aryl-1,2,3,4-tetrahydrobenzo[a]phenanthridines (VIa e)
Comp.
no.
max, nm (log )
VIa
VIb
VIc
VId
VIe
VIf
VIg
VIh
VIi
VIj
VIk
VIl
VIm
VIn
VIo
VIp
VIq
VIr
VIs
203 (4.58), 215 (4.60), 258 (4.68), 275 (4.51), 292 (4.12), 318 (3.50), 336 (3.67), 352 (3.98)
210 (4.58), 248 (4.70), 272 (4.58), 290 (4.29), 308 (3.00), 329 (3.06), 341 (3.10)
203 (4.57), 213 (4.61), 250 (4.72), 274 (4.64), 290 (4.32), 326 (3.46), 349 (3.71), 357 (3.80)
205 (4.59), 216 (4.63), 253 (4.80), 348 (3.74), 359 (4.00)
207 (4.54), 215 (4.60), 250 (4.70), 277 (4.62), 289 (4.30), 349 (3.68), 360 (4.02)
206 (4.51), 217 (4.58), 248 (4.73), 275 (4.65), 292 (4.31), 320 (3.40), 340 (3.70), 354 (3.90)
263 (4.64), 278 (4.49), 340 (3.70), 358 (3.73)
215 (4.34), 252 (4.60), 272 (4.52), 294 (4.30), 318 (3.50), 346 (3.65), 352 (3.71)
213 (4.30), 256 (4.62), 273 (4.50), 296 (4.27), 315 (3.38), 348 (3.50), 356 (3.82)
208 (4.52), 214 (4.59), 253 (4.68), 275 (4.60), 287 (4.33), 313 (3.40), 330 (3.80), 348 (4.00)
206 (4.48), 212 (4.50), 250 (4.60), 271 (4.62), 290 (4.32), 312 (3.37), 340 (3.75), 352 (3.90)
213 (4.34), 253 (4.63), 276 (4.64), 289 (4.25), 311 (3.50), 336 (3.70), 354 (3.80)
206 (4.52), 215 (4.60), 252 (4.78), 274 (4.60), 295 (4.32), 346 (3.70), 357 (4.00)
207 (4.50), 214 (4.57), 252 (4.65), 275 (4.60), 287 (4.33), 312 (3.39), 330 (3.68), 346 (3.94)
203 (4.56), 215 (4.58), 253 (4.64), 274 (4.00), 290 (4.28), 310 (3.42), 328 (3.67), 350 (3.92)
203 (4.61), 218 (4.61), 254 (4.70), 323 (3.52), 338 (3.73), 352 (3.78)
211 (4.30), 252 (4.59), 272 (4.52), 293 (4.28), 319 (3.50), 346 (3.68), 352 (3.70)
210 (4.30), 252 (4.57), 272 (4.51), 291 (4.27), 317 (3.50), 345 (3.64), 350 (3.68)
213 (4.20), 260 (4.55), 274 (4.50), 295 (4.20), 319 (3.43), 347 (3.52), 354 (3.70)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 2 2001

256
KOZLOV, BASALAEVA
max, nm (log )
Table 4. (Contd.)
Comp.
no.
VIt
VIu
VIv
VIw
VIx
VIy
VIz
VI
212 (4.10), 256 (4.34), 270 (4.28), 349 (3.30), 356 (3.80)
206 (4.30), 217 (4.08), 252 (4.28), 272 (4.00), 294 (4.15), 315 (3.70), 330 (3.27), 355 (3.50)
208 (4.28), 214 (4.34), 256 (4.58), 270 (4.10), 291 (4.10), 313 (3.49), 337 (3.42), 354 (3.60)
216 (4.28), 250 (4.62), 270 (4.50), 296 (4.00), 315 (3.51), 348 (3.60), 353 (3.70)
205 (4.60), 217 (4.58), 253 (4.64), 294 (4.10), 320 (3.40), 330 (3.70), 350 (3.80)
206 (4.58), 215 (4.53), 254 (4.60), 293 (4.00), 322 (3.43), 332 (3.70), 350 (3.78)
213 (4.30), 255 (4.40), 290 (4.20), 319 (3.50), 346 (3.20), 352 (3.70)
210 (4.40), 262 (4.57), 276 (4.53), 290 (4.26), 315 (3.60), 347 (3.50), 354 (3.72)
were separated, washed with 25% ammonia, dried,
and recrystallized from ethanol.
7. Watts, W.J., Lawler, C.P., and Knoerzer, T., Eur. J.
Pharmacol., 1993, vol. 239, pp. 271 276.
8. Martines, R., Toscano, R., Lingaza, J.E., and San-
chez, H., J. Heterocycl. Chem., 1992, vol. 29,
pp. 1385 1389.
Method II (for VIv VI ). Aldehyde IIIv III and
0.01 mol of 2-naphthylamine (I) in 50 ml ethanol
were heated on a water bath at 90 C for 1 2 h. After
cooling, 0.03 mol of cyclohexanone II and 5 6 drops
of HCl were added, and heating was continued for an
additional 1.5 2 h. The precipitate that formed was
separated, washed with 25% ammonia, dried, and re-
crystallized from ethanol.
9. Henry, T.A., The Plant Alkaloids, London, 1949,
4th ed. Translated under the title Khimiya rastitel’-
nykh alkaloidov, Moscow: Goskhimizdat, 1965, p. 547.
10. Jpn. Patent 20862, 1965, Ref. Zh. Khim., 1968,
19N395.
11. Kozlov, N.S., Vorob’eva, G.V., and Bychkova, G.S.,
Izv. Akad. Nauk BSSR, Ser. Khim. Nauk, 1969, no. 5,
pp. 80 86.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 2 2001