Reduction of Acridine and 9-Chloroacridine with Red Phosphorus in the KOH/DMSO System

Article abstract of DOI:10.1134/S001250081907005X

Abstract: Acridine reacts with red phosphorus in the KOH/DMSO(H₂O) system on heating (100°C, 3 h) to give 9,10-dihydroacridine regioselectively in quantitative yield. Under similar conditions, 9-chloroacridine reacts with P_red/KOH/DMSO(H₂O) system to afford 9,10-dihydroacridine and acridone in 51 and 40% yield, respectively.

Full text of DOI:10.1134/S001250081907005X

ISSN 0012-5008, Doklady Chemistry, 2019, Vol. 487, Part 1, pp. 177–179. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Doklady Akademii Nauk, 2019, Vol. 487, No. 2.
CHEMISTRY
Reduction of Acridine and 9-Chloroacridine with Red Phosphorus
in the KOH/DMSO System
a
a
a
a
a,
V. A. Kuimov , N. K. Gusarova , S. F. Malysheva , T. V. Kon’kova , and Academician B. A. Trofimov *
Received December 24, 2018
Abstract—Acridine reacts with red phosphorus in the KOH/DMSO(H O) system on heating (100°C, 3 h) to
2
give 9,10-dihydroacridine regioselectively in quantitative yield. Under similar conditions, 9-chloroacridine
reacts with P /KOH/DMSO(H O) system to afford 9,10-dihydroacridine and acridone in 51 and 40% yield,
red
2
respectively.
DOI: 10.1134/S001250081907005X
By the example of 2-bromo- and 2-chloropyridines system leads to dihydroacridine (2) in quantitative
[
1–3], we have recently shown that haloazines react yield (Scheme 2).
with elemental phosphorus in the superbasic
The reduction of 9-chloroacridine 1 and acridine 3
о
KOH/DMSO system on heating (100–125 C, 3 h) to in the P /KOH/DMSO(H O) system to the corre-
red
2
give tris(2-pyridyl)phosphine in 62 and 69% yield,
respectively
sponding 9,10-dihydro derivatives 2 and 4 may be
explained by the following scheme that includes sev-
eral stages. At the first stage, elemental phosphorus
under the action of the superbase produces phospho-
rus-containing nucleophiles: polyphosphide anion A
and polyphosphinite B [5, 6]. Next, polyphosphide
anions A undergo single-electron transfer (SET) to
form unstable anion radical of 9-chloroacridine (C),
which readily decomposes to chloride anion and acri-
dine radical (D). The latter can abstract hydrogen
atom from polyphosphinite B or DMSO to give neu-
tral acridine molecule. Electron transfer from anion A
or anion radical C to acridine molecule leads to forma-
tion of anion radical E whose protonation with water
It was found, however, that 9-chloroacridine (1)
under similar conditions (100°C, 3 h, KOH/DMSO)
did not undergo phosphorylation by red phosphorus,
i.e., produced no C–P bonds. This reaction leads to
9
,10-dihydroacridine (2) (a product of reductive
dehalogenation of 9-chloroacridine) and acridone (3).
The latter compound seems to result from the initial
alkaline hydrolysis of 9-chloroacridine to 9-hydroxy-
acridine [4], which readily transforms into acridone.
The yield of compounds 2 and 3 is 51 and 40%,
respectively (Scheme 1).
The general character of this reduction of 9-chlo- produces dihydroacridine radical F. The subsequent
roacridine to 9,10-dihydroacridine was demonstrated electron transfer from polyphosphide anion A to F
by the example of unsubstituted acridine (4) whose gives anion G whose protonation with water affords
heating (100°C, 3 h) in the P /KOH/DMSO(H O) the target 9,10-dihydroacridine 2 (Scheme 3).
red
2
Cl
O
Pred/KOH/DMSO(H2O)
+
100°C, 3 h, Ar
N
N
H
N
H
1
2, 51%
3, 40%
Scheme 1.
aFavorskii Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, 664033 Russia
e-mail: boris_trofimov@irioch.irk.ru
*
177

1
78
KUIMOV et al.
ing with a 1–2% aqueous NaOH solution and water,
Pred/KOH/DMSO(H2O)
dried under reduced pressure, and stored under N . All
2
100°C, 3 h, Ar
experiments were carried out in an argon atmosphere.
N
N
H
Reaction of 9-chloroacridine with red phospho-
4
2, 95%
rus/KOH/DMSO(H O) system. A mixture of red
2
phosphorus (0.65 g, 20.97 mmol), 9-chloroacridine
(
0.744 g, 3.49 mmol), KOH · 0.5H O (1.50 g,
Scheme 2.
2
1
1.77 mmol), and H O (0.125 mL, 10.9 mmol) in
2
DMSO (16 mL) was stirred for 3 h at 100°C in an
argon atmosphere. The reaction mixture was cooled to
ambient temperature, filtered using a Schott sintered
Thus, using the original reaction of acridine reduc-
tion with red phosphorus in the KOH/DMSO(H O)
2
system, we have developed a convenient and efficient disc filter funnel, and DMSO was removed under
method for the synthesis of 9,10-dihydroacridine, reduced pressure. The resultant residue was washed
which is widely used as a hydrogen donor solvent or a with water (3 × 15–20 mL), and dried under reduced
reagent for hydrocracking of high-density oils and pressure to give 0.719 g of a mixture of products (dark
coals [7–10], antioxidants for polymer compositions brown powder). The powder was washed with chloro-
[
7, 11, 12], and building blocks in the synthesis of form (3 × 10 mL) and filtered off. The chloroform was
innovative materials [13–15].
removed to give 0.32 g (51%) of 9,10-dihydroacridine
as a cream-colored powder, mp 169–170°C.
1
H NMR (CDCl , δ, ppm): 4.04 (s, 2H, CH ),
3
2
EXPERIMENTAL
5
.93 (br s, 1H, NH), 6.65 (d, 2H, Ar), 6.83 (t, 2H, Ar),
1H and 31P NMR spectra were recorded on a 7.08 m (4H, Ar).
1
Bruker DPX-400 spectrometer operating at 400.1 ( H)
13
9
4,5
C NMR (CDCl , δ, ppm): 31.3 (C ), 113.4 (C ),
3
3
1
and 161.98 ( P) MHz in CDCl solutions using
12
2,7
1,8
3,6
3
31
1
1
20.0 (C ), 120.6 (C ), 127.0 (C ), 128.6 (C ),
40.2 (C ).
1
HMDS ( H) and 85% H PO ( Р) as references.
11
3
4
GC–MS was performed on an Agilent Technologies
890N/5975C instrument, HP-5MS column
0.25 mm × 30 m × 0.25 μm), helium as a carrier gas,
For C H N anal. calcd. (%): C, 86.15; H 6.12.
13
11
6
Found (%): C, 86.10; H, 6.23.
(
ionizing voltage 70 eV. Elemental analysis was per-
Acridone (0.27 g, 40%) as a crystalline matter was
formed on a Flash EA 1112 Series analyzer. Red phos- isolated from the residue and characterized by GC–
1
phorus (KSAN “SIA,” China) was purified by wash- MS and H NMR.
Cl
−OH
B
N
P P
P−
N
Cl
N
N
−Cl−
O
SET
−
PH
A
O
P
Pred-fragment
P
B
C
D
A
H2O
−HO−
A
H2O
−HO−
−
−
N
N
N
2
N
SET
SET
P
P
E
F
G
P
P
P P
Recombination
O
Recombination
P
+
P
(O)Pred
Scheme 3.
DOKLADY CHEMISTRY
Vol. 487
Part 1
2019

REDUCTION OF ACRIDINE AND 9-CHLOROACRIDINE
179
FUNDING
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This work was supported by the Russian Foundation for
Basic Research (project no. 17–03–00739).
6
. Trofimov, B.A. and Gusarova, N.K., Mendeleev Com-
mun., 2009, no. 6, pp. 295–302.
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. Serrano, D.P., Aguado, J., Vicente, G., and Sanchez,
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199.
This work was performed using equipment of the Shared
Facility Center, Baikal Analytical Center, Siberian Branch,
Russian Academy of Sciences.
8
. Yang, Y., Wang, Q., Chen, H., and Zhang, X., Fuel,
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DOKLADY CHEMISTRY Vol. 487 Part 1 2019