Reactions of 1,5-diketones with 2-aminobenzyl alcohol and 2-aminomethylaniline and behavior of the products in oxidative coupling

Article abstract of DOI:10.1134/S1070428012090059

Reactions of some 1,5-diketones with 2-aminobenzyl alcohol and 2-aminomethylaniline follow double cyclization scheme with formation of pyridobenzoxazine and pyridoquinazoline derivatives, respectively. Oxidative coupling of the cyclization products with C

Full text of DOI:10.1134/S1070428012090059

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 9, pp. 1180–1186. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © O.Yu. Slabko, A.V. Kachanov, V.A. Kaminskii, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 9,
pp. 1182–1187.
Reactions of 1,5-Diketones with 2-Aminobenzyl Alcohol
and 2-Aminomethylaniline and Behavior of the Products
in Oxidative Coupling
O. Yu. Slabko, A. V. Kachanov, and V. A. Kaminskii
Far East Federal University, ul. Oktyabr’skaya 27, Vladivostok, 690600 Russia
e-mail: slabko@chem.dvgu.ru
Received November 15, 2011
Abstract—Reactions of some 1,5-diketones with 2-aminobenzyl alcohol and 2-aminomethylaniline follow
double cyclization scheme with formation of pyridobenzoxazine and pyridoquinazoline derivatives,
respectively. Oxidative coupling of the cyclization products with CH acids occurs at the 4-position of the
pyridine ring.
DOI: 10.1134/S1070428012090059
Reactions of 1,5-dicarbonyl compounds with such
1,2-binucleophiles as o-phenylenediamine, o-amino-
phenol, and 2-aminoethanol have been extensively
studied. These reactions lead to the formation of
double cyclization products belonging to the pyrido-
[1,2-a]benzimidazole and pyrido[3,2-a](benz)oxazole
series [1, 2]. Successful double cyclization was also
performed with some 1,3-binucleophiles, in particular
with 3-aminopropan-1-ol and anthranilic acid [2], and
derivatives of pyrido[2,1-b]oxazine and pyrido[1,2-a]-
benzoxazin-6-one were obtained.
an analog of 2-aminomethylaniline (Ib) with a 1,5-di-
carbonyl compound, 2-(2-oxoethyl)benzaldehyde, in
which successive closure of two six-membered rings
led to pyridobenzodiazine system [12].
In the present work we studied the behavior of
some 1,5-diketones in reactions with compounds Ia
and Ib. Taking into account the data of [1, 2], these
reactions might be expected to follow double cycliza-
tion scheme with successive closure of hydrogenated
pyridine and 1,3-oxazine (pyrimidine) rings.
As 1,5-dicarbonyl compounds we used diketones
IIa–IIe; instead of diketone IIc, the reactions were
carried out with more accessible product of its intra-
molecular aldolization–crotonization, hydroxy ketone
III, which generated IIc via retro-aldol reaction.
Compound III has already been used as synthetic
equivalent of IIc in reactions with binucleophiles [13]
(Scheme 1). The reactions of diketones IIa, IIb, IId,
and IIe with 2-aminobenzyl alcohol (Ia) were carried
out at 60–70°C, while compound III reacted with Ia in
boiling xylene over a period of 3–4 days. Diketones
IIb, IId, and IIe reacted with 2-aminomethylaniline
(Ib) on heating in boiling benzene (15–16 h), whereas
the reaction of IIa with Ib occurred at room tempera-
ture. In all cases, p-toluenesulfonic acid was added as
catalyst.
Reactions of such 1,3-binucleophiles as 2-amino-
benzyl alcohol and 2-aminomethylaniline with 1,5-di-
carbonyl compounds were not reported. It is well
known that reactions of 2-aminobenzyl alcohol (Ia),
2-aminomethylaniline (Ib), and their analogs with
monocarbonyl compounds generally involve cycliza-
tion to 1,3-benzoxazine [3, 4] and 1,3-benzodiazine
structures [5, 6]. 1,2- and 1,3-Dicarbonyl compounds
reacted with 2-aminobenzyl alcohol (Ia) at one car-
bonyl group, leading to diimines and enamines, respec-
tively [7, 8]. Reactions of 2-aminomethylaniline (Ib)
with 1,2-dicarbonyl compounds produced benzodi-
azepines or benzodiazines if only one carbonyl group
was involved [9]. The cyclization with 1,3-dicarbonyl
compounds also occurred at one carbonyl group with
formation of 1,3-benzodiazines [10], whereas 1,4-di-
carbonyl compounds gave rise to benzopyrimidine
derivatives as a result of double cyclization [11]. We
have found only one reported example of reaction of
All reactions followed the double cyclization
scheme; however, they required a longer time and were
characterized by lower selectivity and lower yields, as
1180

REACTIONS OF 1,5-DIKETONES WITH 2-AMINOBENZYL ALCOHOL
1181
Scheme 1.
H
B
H
A
N
O
O
N
+
5
IV
V
Ph
H
O
N
VI
O
N
N
HO
R3
NH2
R2
R1
R4
R5
VII
+
HX
O
O
Ia, Ib
Ph
IIa–IIe
HN
N
HN
N
+
IIc
VIII
IX
O
OH
III
Ph
H
HN
N
Ph
X
Ph
Ph
N
HN
N
NH2
XI
I, X = O (a), NH (b); II, R1R2 = R4R5 = (CH2)4, R3 = H (a); R1R2 = R4R5 = (CH2)3, R3 = H (b); R1R2 = R4R5 = (CH2)4, R3 = Ph (c);
R1R2 = (CH2)4, R3 = R5 = Ph, R4 = H (d); R1R2 = (CH2)4, R3 = Ph, R4R5 = 1,2-(3,4-dihydronaphtho) (e).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 9 2012

SLABKO et al.
1182
compared to analogous reactions of the same diketones
with o-aminophenol and o-phenylenediamine. Amino
alcohol Ia reacted only with symmetric 1,5-diketones
IIa–IIc, while fatty–aromatic diketones IId and IIe
failed to react even under prolonged heating. Diamine
Ib reacted only with diketones IIa, IId, and IIe. Non-
equivalence of the primary amino groups in Ib and
unsymmetrical structure of diketones IId and IIe gave
rise to regioselectivity problem in both substrate and
reagent. Prolonged heating of the reaction mixture of
compounds IIa and Ib resulted in the formation of
a mixture of cyclization products VIII and IX which
could not be separated by chromatography (similar
Rf values).
a five-membered ring was reported previously [1];
opening of imidazole ring was not observed under
analogous conditions.
1
The H NMR spectrum of mixture VIII/IX (2:3)
contained four doublets belonging to nonequivalent
benzylic protons, which was interpreted as formation
of two isomers corresponding to different cyclization
pathways. This assumption was confirmed by oxida-
tion of mixture VIII/IX with carbon tetrachloride on
heating in boiling benzene according to the proce-
1
dure described in [14] (Scheme 2). In the H NMR
spectrum of pyridinium salt mixture XII/XIII (2:3)
thus obtained we observed singlets from benzylic pro-
tons at δ 4.46 and 5.63 ppm. Comparison with the
spectral data for N-benzyloctahydroacridinium salt
[15] which displayed benzylic proton signal at
δ 5.80 ppm (s) allowed us to assign the signal at
δ 5.63 ppm to isomer XIII, and that at δ 4.46 ppm, to
isomer XII.
The IR spectra of IV–VII lacked absorption band
typical of OH stretching vibrations, whereas com-
pounds VIII–XI displayed an absorption band assign-
able to secondary amino group in support of their
cyclic structure. Also, a single absorption band belong-
ing to enamino group was observed in the region
1629–1677 cm–1 (the spectra of dihydropyridine struc-
tures with an opened ring contain two bands in that
region).
1
In the H NMR spectrum of X, the doublet signal
from the aromatic 4-H proton is displaced appreciably
upfield (δ 5.91 ppm). According to ab initio quantum-
chemical calculations (6-31G* basis set, gas phase) for
analogous double cyclization product of diketone IId
with o-phenylenediamine, the 4-H proton is shielded
due to magnetically anisotropic effect of the 6-substit-
uent [16]. No such upfield shift was observed in the
spectrum of XI; therefore, the latter was assigned the
structure resulting from pyridine ring closure with
participation of the benzylamino group; in this case,
protons in the aromatic residue of diamine Ib are not
shielded by fairly distant phenyl group.
1
In the H NMR spectra of IV–VI and VIII–X we
observed signals from two nonequivalent benzylic
protons (originating from compounds Ia and Ib) as
two doublets in the region δ 4.16–4.87 ppm, 2J = –12.6
to –19.0 Hz, which correspond to conformationally
rigid benzoxazine (benzopyrimidine) structure. Com-
pounds IV and V displayed in the 1H NMR spectra two
sets of signals; presumably, they were formed as mix-
tures of stereoisomers with cis- and trans-junction of
the A and B rings (isomer ratio 2.7:1). According to
the IR data, crystalline compounds VII and XI (KBr)
have cyclic structure (closed oxazine and pyrimidine
rings respectively). In going to solution in CDCl3 for
The structure of compound VI was unambiguously
proved by X-ray analysis [17]. The formation of one
isomer with cis-junction of the A and B rings is likely
to be determined by additional stabilization effect
produced by the phenyl substituent in position 3. On
the basis of these data we presumed cis-junction of the
A and B rings in structurally related double cyclization
products X and XI.
1
recording H NMR spectra, opening of the heteroring
occurs, and the corresponding benzylic protons be-
come equivalent (a singlet is observed). Ready opening
of partly hydrogenated oxazine ring in the double cy-
clization products obtained from diketones containing
Scheme 2.
CCl4, PhH
NH2
N
NH2
N
VIII
+
IX
+
Cl–
Cl–
XII
XIII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 9 2012

REACTIONS OF 1,5-DIKETONES WITH 2-AMINOBENZYL ALCOHOL
1183
Scheme 3.
[O]
N
N
N
HN
N
N
XIV
A
We previously showed that double cyclization prod-
ucts like XIV (derived from 1,5-diketones and o-phen-
ylenediamine) are capable of undergoing oxidation and
oxidative coupling with a number of amines and CH
acids; these reactions afforded heterocyclic p-quinone
monoimines, p-quinone diimines and p-methylene-
quinone imines, respectively [18, 19]. A probable
mechanism of oxidative coupling implied initial
formation of pyridobenzimidazolium cation A stabi-
lized by the donor vinylamino fragment (Scheme 3).
In order to extend the series of possible substrates
for oxidative coupling and prove (or disprove) its
mechanism proposed previously, we examined oxida-
tive coupling of isomer mixture IV/V with malono-
nitrile and indan-1,3-dione in ethanol in the presence
of MnO2 activated according to [20] (Scheme 4). The
reaction was much slower (3 days at room tempera-
ture) and considerably less selective, and it followed
a different pathway. We succeeded in isolating by
column chromatography non-quinoid oxidative cou-
pling products XV and XVI in a poor yield.
pyridine E (Scheme 5). The final step is oxazine ring
closure, and the substituent in the γ-position of the
pyridine ring favors cis-junction of the A and B rings.
However, we failed to properly confirm the proposed
mechanism of oxidative coupling by carrying out the
reaction of malononitrile with a simpler substrate,
N-benzyldecahydroacridine, for the reaction was ab-
solutely nonselective.
The IR spectrum of XV contained an absorption
band at 2207 cm–1 due to stretching vibrations of
conjugated cyano group, and compound XVI dis-
played an absorption band at 1717 cm–1 due to con-
jugated carbonyl group in the five-membered ring.
Enamine absorption band had low intensity and was
displaced toward lower frequencies, as compared to
the initial compounds, as a result of extension of the
conjugation chain. The IR spectra of both compounds
1
XV and XVI lacked OH absorption. In the H NMR
spectra of XV and XVI benzylic protons in the oxazine
ring resonated as doublets with the corresponding
geminal coupling constant, whereas no signals assign-
able to quinoid protons were present; therefore,
quinoid structure was unambiguously ruled out.
Taking into account published data on nucleophilic
addition to pyridinium salts at the γ-position [21, 22],
we presumed that the reaction involves reversible
opening of the oxazine ring with formation of dihydro-
pyridine structure B, its subsequent oxidation to pyr-
idinium zwitterion C, and attack on the latter by CH
acid anion at the γ-position to give nucleophilic addi-
tion product D which is readily oxidized to dihydro-
EXPERIMENTAL
The IR spectra were recorded in KBr on a Spectrum
1
BX-II spectrometer. The H NMR spectra were meas-
ured on a Bruker AC-250 spectrometer operating at
Scheme 4.
R1
R2
H
H
CH2R1R2, MnO2
CH2R1R2, MnO2
IV
+ V
O
N
O
N
R1
R2
XV, XVI
XV, R1 = R2 = CN; XVI, R1R2 = phthaloyl.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 9 2012

SLABKO et al.
1184
Scheme 5.
[O]
N
N
N
IV
+ V
HO
O
O
B
C
R1
R2
R1
R2
CHR1R2
[O]
N
N
XV, XVI
O
O
D
E
250 MHz; tetramethylsilane was used as internal refer-
ence, and CDCl3, as solvent. The elemental composi-
tions were determined on a Flash EA 1112 CHN/
MAS200 CHN analyzer. HPLC analyses were run on
an HP 1100 LC/MSD instrument equipped with
a 4×125-mm Hypersil ODS column and a diode array
detector (eluent propan-2-ol–water, 50:50, flow rate
0.3 ml/min; temperature 55°C; API-ES ion source,
positive polarity). The melting points were determined
in capillaries on a Boetius melting point apparatus. The
progress of reactions and the purity of products were
monitored by TLC on Silufol UV-254 and Sorbfil
plates using petroleum ether–ethyl acetate as eluent.
The products were isolated and purified by column
chromatography and preparative thin-layer chromatog-
raphy (25×30-cm plates coated with aluminum oxide
of activity grade II according to Brockmann; layer
thickness 1.5 mm, sample weight 0.25 g).
distilled off under reduced pressure, and the residue
was subjected to column chromatography using petro-
leum ether as eluent (IV–IX); in the syntheses of X
and XI, the residue was treated with 5 ml of ethanol,
and almost pure product separated in 10 h and was
recrystallized from ethanol. Compounds IV, V, VIII,
and IX were isolated as oily substances, and the others
were crystalline substances.
7,8,9,10,10a,11,12,13,14,15-Decahydro-5H-[3,1]-
benzoxazino[2,1-e]acridine [(6aS,10aS)-IV, cis-A,B;
(6aR,10aS)-V, trans-A,B]. Yield 32 %. IR spectrum:
1
ν 1676 cm–1 (C11a=C15a). H NMR spectrum, δ, ppm:
1.00–2.30 m (19H), 4.52 d (1H, 5-Hax in IV, J =
–13.2 Hz), 4.58 d (1H, 5-Heq in IV, J = –13.2 Hz),
4.71 d (1H, 5-Hax in V, J = –13.5 Hz), 4.87 d (1H,
5-Heq in V, J = –13.5 Hz), 6.74 d (1H, 1-H, J = 8.0 Hz),
6.87 t (1H, 3-H, J = 8.0 Hz), 7.02 d (1H, 4-H, J =
8.0 Hz), 7.13 t (1H, 2-H, J = 8.0 Hz). Found, %:
C 79.95; H 8.16; N 5.08. m/z 296 [M + H]+. C20H25NO.
Calculated, %: C 81.31; H 8.53; N 4.74. M 295.42.
All compounds were synthesized following a gen-
eral procedure; only their isolation and purification
procedures were different. Commercially available
reagents (Aldrich, Fluka) were used without additional
purification.
11-Phenyl-7,8,9,10,10a,11,12,13,14,15-decahy-
dro-5H-[3,1]benzoxazino[2,1-e]acridine (VI). Yield
41%, mp 160–162°C. IR spectrum: ν 1678 cm–1
Compounds IV–XI (general procedure). Com-
pound IIa, IIb, IId, or IIe, 1.0 mmol, was dissolved in
15 ml of benzene (compound IIc was dissolved in
15 ml of p-xylene), 1.1 mmol of amine Ia or Ib and
0.01 mmol of p-toluenesulfonic acid were added, and
the mixture was kept for 150 h at room temperature
(VII–IX), heated for 90 h at 60°C on a water bath (IV,
V), or heated under reflux for 15 h (X, XI) or 35 h in
a flask equipped with a Dean–Stark trap (VI) until the
initial compound disappeared (TLC). The solvent was
1
(C11a=C15a). H NMR spectrum, δ, ppm: 1.50–2.00 m
(16H), 2.65 d (1H, 15-Heq, J = 16.0 Hz), 3.04 d (1H,
11-H, J = 9.0 Hz), 4.40 d (1H, 5-Hax, J = –12.6 Hz),
4.55 d (1H, 5-Heq, J = –12.6 Hz), 6.80 t (2H, 7-H, 8-H,
J = 8.0 Hz), 7.00–7.24 m (7H, Harom). Found, %:
C 83.92; H 7.69; N 3.70. m/z 372 [M + H]+. C26H29NO.
Calculated, %: C 84.06; H 7.87; N 4.31. M 371.51.
7,8,9,9a,10,11,12,13-Octahydro-5H-dicyclopenta-
[2,3:5,6]pyrido[1,2-a][3,1]benzoxazine (VII). Yield
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 9 2012

REACTIONS OF 1,5-DIKETONES WITH 2-AMINOBENZYL ALCOHOL
1185
44%, mp 86–88°C. IR spectrum: ν 1678 cm–1
acridinium chlorides XII and XIII. Yield 89%.
1H NMR spectrum, δ, ppm: 1.25–3.20 m (16H), 3.63 d
(1H, 4-Heq in XII, J = –14.2 Hz), 4.46 s (2H, CH2NH2
in XII), 5.63 s (2H, CH2N in XIII), 6.50–7.78 m
(Harom), 7.83 s (1H, 9-H in XIII), 7.94 s (1H, 9-H
in XII).
1
(C10a=C13a). H NMR spectrum, δ, ppm: 1.59–2.79 m
(14H), 4.92 br.s (2H, 5-H), 6.91–7.16 m (4H, Harom).
Found, %: C 80.98; H 8.23; N 5.20. m/z 268 [M + H]+.
C18H21NO. Calculated, %: C 80.86; H 7.92; N 5.24.
M 267.37.
Compounds XV and XVI. Stereoisomer mixture
IV/V, 1.0 mmol, was dissolved in 8 ml of ethanol,
1.2 mmol of malononitrile or indan-1,3-dione was
added, the mixture was stirred until it became homo-
geneous, 15 mmol of activated MnO2 was added, and
the mixture was kept at room temperature until the
initial compound disappeared (TLC; 72 h in the syn-
thesis of XV or 120 h in the synthesis of XVI). The
precipitate of MnO2 was filtered off and washed with
ethanol until colorless washings. The filtrate was com-
bined with the washings and evaporated, the residue
was diluted with water, and the precipitate was filtered
off, washed with water (3×5 ml), dried, and subjected
to column chromatography on aluminum oxide using
petroleum ether–ethyl acetate (2:1) as eluent. A yellow
fraction was collected and evaporated to isolate com-
pound XV or XVI as yellow crystals.
5,6,7,8,9,10,10a,11,12,13,14,15-Dodecahydro-
quinazolino[2,1-e]acridine (VIII) and 5,6,7,8,9,9a,-
10,11,12,13,14,16-dodecahydroquinazolino[2,3-e]-
acridine (IX). Yield 31%. IR spectrum, ν, cm–1: 3415
(NH), 1668 (C=C). 1H NMR spectrum, δ, ppm: 1.25–
2.50 m (19H), 4.16 d (1H, 5-Hax in VIII, J =
–17.3 Hz), 4.26 d (1H, 5-Heq in VIII, J = –17.3 Hz),
4.23 d (1H, 16-Hax in IX, J = –19.0 Hz), 4.31 d (1H,
16-Heq in IX, J = –19.0 Hz), 6.59 m (2H, 2-H, 3-H),
6.85 d (1H, 1-H, J = 7.2 Hz), 7.00 d (1H, 4-H, J =
7.3 Hz). Found, %: C 81.85; H 9.28; N 9.32. m/z 295
[M + H]+. C20H26N2. Calculated, %: C 81.59; H 8.90;
N 9.51. M 294.43.
6,8-Diphenyl-8,8a,9,10,11,12,13,14-octahydro-
quinolino[1,8a-a]quinazoline (X). Yield 34%,
mp 175–176°C. IR spectrum, ν, cm–1: 3404 (NH),
1
1646 (C6=C7). H NMR spectrum, δ, ppm: 1.20–
8,9,10,10a,12,13,14,15-Octahydro-5H-[3,1]benz-
oxazino[2,1-e]acridin-11(7H)-ylidenemalononitrile
(XV). Yield 23%, mp 165–167°C. IR spectrum, ν,
cm–1: 2207 (CN), 1605 (C11a=C15a). 1H NMR spectrum,
δ, ppm: 1.20–2.50 m (17H), 4.77 d (1H, 5-Hax, J =
–12.3 Hz), 4.89 d (1H, 5-Heq, J = –12.3 Hz), 6.97 d
(1H, 1-H, J = 8.0 Hz), 7.13 t (1H, 3-H, J = 8.0 Hz),
7.18 d (1H, 4-H, J = 8.0 Hz), 7.22 t (1H, 2-H, J =
8.0 Hz). Found, %: C 77.39; H 6.24; N 11.85. m/z 358
[M + H]+. C23H23N3O. Calculated, %: C 77.28; H 6.49;
N 11.76. M 357.45.
2.35 m (9H), 3.33 d.d (1H, 8-H, J = 9.6, 5.5 Hz),
3.41 s (1H, NH), 4.00 d (1H, 14-Hax, J = –16.8 Hz),
4.16 d (1H, 14-Heq, J = –16.8 Hz), 4.73 d (1H, 7-H, J =
5.5 Hz), 5.91 d (1H, 4-H, J = 7.8 Hz), 6.51 t (1H, 3-H,
J = 7.7 Hz), 6.58 d (1H, 1-H, J = 7.3 Hz), 6.93 t (1H,
2-H, J = 7.4 Hz), 7.15–7.40 m (10H, Harom). Found, %:
C 85.50; H 7.06; N 7.25. m/z 392 [M + H]+. C28H28N2.
Calculated, %: C 85.67; H 7.19; N 7.14. M 392.54.
10-Phenyl-5,6,7,8,9,9a,10,11,12,18-decahydro-
benzo[c]quinazolino[3,2-f]acridine (XI). Yield 55%,
mp 162–164°C. IR spectrum, ν, cm–1: 3430 (NH),
1
1630 (C10a=C16b). H NMR spectrum, δ, ppm: 1.2–
2-{8,9,10,10a,12,13,14,15-Octahydro-5H-[3,1]-
benzoxazino[2,1-e]acridin-11(7H)-ylidene}-1H-
indene-1,3(2H)-dione (XVI). Yield 18%, mp 100–
102°C. IR spectrum, ν, cm–1: 1717 (C=O), 1612
2.64 m (13H), 3.14 s (1H, 10-H), 4.37 br.s (2H, 18-H),
6.52 t (1H, 2-H, J = 7.6 Hz), 6.76 d (1H, 4-H, J =
7.6 Hz), 6.93 t (1H, 3-H, J = 7.6 Hz), 7.14–7.36 m
(9H, Harom), 7.46 d (1H, 1-H, J = 7.6 Hz). Found, %:
C 86.34; H 7.42; N 6.55. m/z 419 [M + H]+. C30H30N2.
Calculated, %: C 86.08; H 7.22; N 6.69. M 418.57.
1
(C11a=C15a). H NMR spectrum, δ, ppm: 1.25–2.10 m
(17H), 4.73 d (1H, 5-Hax, J = –12.5 Hz), 4.76 d (1H,
5-Heq, J = –12.5 Hz), 6.92 d (1H, 1-H, J = 8.0 Hz),
7.06 t (1H, 3-H, J = 8.0 Hz), 7.12 d (1H, 4-H, J =
8.0 Hz), 7.17 t (1H, 2-H, J = 8.0 Hz), 7.50–7.73 m
(4H, Harom). Found, %: C 79.45; H 6.39; N 2.96.
m/z 438 [M + H]+. C29H27NO3. Calculated, %: C 79.61;
H 6.22; N 3.20. M 437.53.
10-[2-(Aminomethyl)phenyl]-1,2,3,4,5,6,7,8-octa-
hydroacridinium chloride (XII) and 10-(2-amino-
benzyl)-1,2,3,4,5,6,7,8-octahydroacridinium chlo-
ride (XIII). Mixture VIII/IX, 1.0 mmol, was dis-
solved in 10 ml of benzene, 4.0 mmol of carbon tetra-
chloride was added, and the mixture was heated for 3 h
under reflux until the initial compounds disappeared
(TLC). The solvent was distilled off under reduced
pressure, and the crystalline residue was a mixture of
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SLABKO et al.
1186
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