Unexpected Reaction of Secondary Phosphine Chalcogenides with Acridine

Article abstract of DOI:10.1134/S1070363219030290

Secondary phosphine chalcogenides reacted with acridine under mild conditions according to the nucleophilic addition scheme to form 9-chalcogenophosphoryl-9,10-dihydroacridines.

Full text of DOI:10.1134/S1070363219030290

ISSN 1070-3632, Russian Journal of General Chemistry, 2019, Vol. 89, No. 3, pp. 543–545. © Pleiades Publishing, Ltd., 2019.
Russian Text © P.A. Volkov, A.A. Telezhkin, N.I. Ivanova, K.O. Khrapova, N.K. Gusarova, B.A. Trofimov, 2019, published in Zhurnal Obshchei Khimii,
2019, Vol. 89, No. 3, pp. 475–478.
LETTERS
TO THE EDITOR
Unexpected Reaction of Secondary Phosphine Chalcogenides
with Acridine
P. A. Volkova, A. A. Telezhkina, N. I. Ivanovaa,
K. O. Khrapovaa, N. K. Gusarovaa, and B. A. Trofimova*
a Favorskii Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
*e-mail: boris_trofimov@irioch.irk.ru
Received November 1, 2018; revised November 1, 2018; accepted November 11, 2018
Abstract—Secondary phosphine chalcogenides reacted with acridine under mild conditions according to the
nucleophilic addition scheme to form 9-chalcogenophosphoryl-9,10-dihydroacridines.
Keywords: acridine, secondary phosphine chalcogenides, nucleophilic addition, 9-chalcogenophosphoryl-9,10-
dihydroacridines
DOI: 10.1134/S1070363219030290
We have recently reported on an original three-
component reaction of azines, secondary phosphine
chalcogenides, and alkyl propiolates exemplified by
pyridines and quinolines [1–3]. The reaction proceeds
under mild conditions (20–72°C, 3–19 h, MeCN) with
regio- and stereoselective formation of the С-phos-
phorylated (E)-N-ethenyl-1,4(or 1,2)-dihydropyridines
(or quinolines) [1–3] (Scheme 1).
chalcogenides with acridine – 9-chalcogenophosphoryl-
9,10-dihydroacridines 2а–2c were formed in 60–65%
yield. Such addition of secondary phosphine chalco-
genides to acridine readily proceeded also in the
absence of methyl propiolate, the yield of dihydro-
acridines 2а–2c being 64–69%. That meant that the
electron-deficient acetylene did not participate in the
reaction even at the intermediate stages (Scheme 2).
At the same time, according to the reference data,
acridine can enter three-component reactions with
methyl propiolate [4] or dimethyl acetylenedicar-
boxylate [5] and some CH- or OH-acids (nitromethane
[4] and methanol [5]) to form the corresponding
functionalized N-ethenyl adducts.
In this study, we attempted to realize that three-
component reaction using acridine as the azine. Ho-
wever, heating (50–52°C) of acridine, secondary phos-
phine chalcogenides 1а–1c, and methyl propiolate in aceto-
nitrile for 4–7 h did not give the expected C9-phos-
phorylated N-ethenyl-9,10-dihydroacridines (Scheme 2).
Under those conditions, methyl propiolate was not
involved in the reaction, but 1 : 1 adducts of phosphine
Therefore, phosphorylation of acridine by
secondary phosphine chalcogenides easily prepared
Scheme 1.
R1
R1
X
P
R3
R1
X
R1
R1
R3
X
H
O
OR2
N
P
N
N
R1
+
P
70−72°C, 7−19 h
20−52°C, 3−8 h
N
MeCN
MeCN
R2O2C
CO2R2
35−75%
47−86%
R1 = Ph, Ph(CH2)2; R2 = Me, Et; R3 = H, Me; X = O, S, Se.
543

544
VOLKOV et al.
Scheme 2.
R
O
O
R
P X
OMe
(or without it)
X
OMe
R
X
H
R
R
P
×
P
+
50−52°C, 4−7 h
50−52°C, 4−7 h
R
MeCN
N
N
N
MeCN
H
2а−2c
CO2Me
1а−1c
Not formed
R = Ph, X = O (а); R = Ph(CH2)2, X = S (b), X = Se (c).
2
4
from elemental phosphorus, styrene, and chalcogens
[6] opens a convenient way to the earlier unknown
phosphorylated dihydroacridines, promising precursors
for the design of drugs [7–9], reagents for preparation
of innovative materials [10, 11], ligands for the
synthesis of metal complexes [12–14], and building
blocks for organic and organoelement synthesis [15–17].
114.2 d (C8a, JCP = 5.6 Hz); 119.0 d (C2,7, JCP
=
5
2.3 Hz); 127.6 d (C3,6, JCP = 2.7 Hz); 128.1 d (Cm,
3JCP = 10.7 Hz); 129.9 d (C1,8, JCP = 3.8 Hz); 131.5 d
3
1
4
(Cipso, JCP = 91.5 Hz); 131.6 d (Cp, JCP = 2.7 Hz);
131.9 d (Cо, 2JCP = 8.7 Hz); 141.8 d (C4a, 3JCP = 3.4 Hz).
15N NMR spectrum (DMSO-d6), δN: –279.6 ppm. 31P
NMR spectrum (DMSO-d6), δP: 30.3 ppm. Found, %:
С 78.89; Н 5.43; N 3.75; P 7.93. С25Н20NOP.
Calculated, %: С 78.73; Н 5.29; N 3.67; P 8.12.
The mentioned experiments were performed under
inert atmosphere (argon). The reactions were
monitored by 31Р NMR spectroscopy.
9-[Bis(2-phenylethyl)phosphorothioyl]-9,10-di-
hydroacridine (2b). Yield 290 mg (64%), yellow
powder, mp 133–135°C. IR spectrum (film), ν, cm–1:
3388, 3289, 3204, 3057, 3029, 2921, 1602, 1484,
1450, 1406, 1301, 1214, 1072, 1033, 906, 835, 737,
703, 646, 603, 470. H NMR spectrum (CDCl3), δ,
ppm: 1.86, 2.10 m (4H, CH2P); 2.76 m (4H, CH2Ph);
4.60 d (1H, CHP, JPH = 15.1 Hz); 6.14 s (1H, NH);
6.75 d [2H, H4,5, J4(5)-3(6) = 7.8 Hz]; 7.04 d. d [2H,
Nucleophilic addition of secondary phosphine
chalcogenides 1а–1c to acridine. 1.0 mmol of
acridine was added to a solution of secondary
phosphine chalcogenide 1а–1c (1.0 mmol) in 3 mL of
acetonitrile. The reaction mixture was stirred at 50–52°C
during 4 h (in the case of phosphine chalcogenide 1c)
or 7 h (in the cases of phosphine chalcogenides 1а, 1b)
until disappearance of the signal of the starting
phosphine chalcogenide (2–23 ppm) in the 31Р NMR
spectrum and appearance of the signal of compounds
2а–2c at 30–60 ppm. The solvent was removed under
reduced pressure, the residue was washed with Et2O
(5×1 mL) via decantation (in the case of dihydro-
acridine 2а) or resedimented from acetone to hexane
(in the cases of dihydroacridines 2b, 2c).
1
2
3
3
3
H2,7, J2(7)-1(8) ≈ J2(7)-3(6) = 7.3 Hz]; 7.15 m (4H, Hо);
7.21 m (2H, H3,6); 7.24 m (2H, Hp); 7.29 m (4H, Hm);
7.37 d [(2H, H1,8, J1(8)-2(7) = 7.3 Hz]. 13C NMR
3
2
spectrum (CDCl3), δC, ppm: 28.7 d (CH2Ph, JCP
=
1
2.9 Hz); 29.2 d (CH2P, JCP = 43.3 Hz); 49.9 d (CHP,
1JCP = 42.2 Hz); 114.3 (C4,5); 115.4 d (C8a, JCP
=
2
3.6 Hz); 121.0 (C2,7); 126.4 (Cp); 128.2 (Cо); 128.7
(Cm); 128.9 d (C3,6, 5JCP = 3.4 Hz); 130.6 d (C1,8, 3JCP
3.2 Hz); 140.0 d (C4a, 3JCP = 3.1 Hz); 141.3 d (Сipso, 3JCP
=
=
9-(Diphenylphosphoryl)-9,10-dihydroacridine (2а).
Yield 263 mg (69%), white powder, mp 218–219°C.
IR spectrum (KBr), ν, cm–1: 3391, 3055, 2903, 1631,
1473, 1435, 1301, 1252, 1181, 1106, 1031, 752, 697,
560, 533. 1H NMR spectrum (DMSO-d6), δ, ppm: 5.40
14.6 Hz). 15N NMR spectrum (CDCl3), δN: –284.1 ppm.
31P NMR spectrum (CDCl3), δP: 59.3 ppm. Found, %:
С 76.53; Н 6.39; N 3.24; P 6.62; S 6.79. С29Н28NPS.
Calculated, %: С 76.79; Н 6.22; N 3.09; P 6.83; S 7.07.
2
d (1H, CHP, JPH = 11.3 Hz); 6.46 d. d [2H, H2,7,
3J2(7)-1(8) ≈ 3J2(7)-3(6) = 7.2 Hz]; 6.62 d [2H, H1,8, 3J1(8)-2(7)
=
9-[Bis(2-phenylethyl)phosphoroselenoyl]-9,10-
dihydroacridine (2c). Yield 330 mg (66%), beige
powder, mp 128–131°C. IR spectrum (film), ν, cm–1:
3392, 3264, 3188, 3058, 3027, 2928, 1607, 1480,
1455, 1405, 1304, 1211, 1069, 1031, 909, 853, 742,
7.2 Hz]; 6.68 d [2H, H4,5, 3J4(5)-3(6) = 8.2 Hz]; 6.98 d. d
3
3
[2H, H3,6, J3(6)-4(5) ≈ J3(6)-2(7) = 7.5 Hz]; 7.41 m (4H,
Hm); 7.54 m (2H, Hp); 7.72 m (4H, Hо); 8.56 s (1H,
NH). 13C NMR spectrum (DMSO-d6), δC, ppm: 45.7 d
1
4
1
(CHP, JCP = 64.0 Hz); 113.6 d (C4,5, JCP = 2.1 Hz);
702, 651, 485. H NMR spectrum (CDCl3), δ, ppm:
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 3 2019

UNEXPECTED REACTION OF SECONDARY PHOSPHINE CHALCOGENIDES
545
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1.95, 2.19 m (4H, CH2P); 2.76 m (4H, CH2Ph); 4.74 d
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[2H, H4,5, J4(5)-3(6) = 7.7 Hz]; 6.97 d. d [(2H, H2,7,
3J2(7)-1(8) ≈ 3J2(7)-3(6) = 7.3 Hz]; 7.09 m (4H, Hо); 7.15 m
(4H, Ph, Ar); 7.21 m (4H, Ph, Ar); 7.44 br. d [2H, H1,8,
3J1(8)-2(7) = 7.3 Hz]. 13C NMR spectrum (CDCl3), δC,
ppm: 29.0 d (CH2P, 1JCP = 36.0 Hz); 29.7 d (d, CH2Ph,
1
2JCP = 2.1 Hz); 49.6 d (CHP, JCP = 34.7 Hz); 114.2 d
4
2
(C4,5, JCP = 2.8 Hz); 115.4 d (C8a, JCP = 4.1 Hz);
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121.7 d (C2,7, JCP = 2.8 Hz); 126.1 (Cp); 128.0 (Cо);
128.3 (Cm); 128.7 d (C3,6, 5JCP = 2.8 Hz); 130.7 d (C1,8,
3JCP = 3.4 Hz); 140.1 d (C4a, JCP = 3.4 Hz); 141.3 d
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δN: –283.1 ppm. 31P NMR spectrum (CDCl3), δP: 53.5
ppm (+d-satellites, JPSe = 709.8 Hz). 77Se NMR
1
spectrum (CDCl3), δSe: –379.9 ppm, d (1JPSe = 709.8 Hz).
Found, %: С 69.43; Н 5.82; N 2.64; P 6.04; Se 15.56.
С29Н28NPSe. Calculated, %: С 69.60; Н 5.64; N 2.80;
P 6.19; Se 15.78.
IR spectra were recorded using a Varian 3100 FT-
IR spectrometer (KBr pellet or thin layer). 1H, 13C, 15N,
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DPX-400 and Bruker AV-400 spectrometers (400.13,
10.62, 40.56, 161.98 and 76.31 МHz, respectively) in
CDCl3 or DMSO-d6, with the following internal
[HMDS (1H, 13C), MeNO2 (15N), Me2Se (77Se)] or
external [85% Н3РО4 (31Р)] references. The signals in
the proton spectra were assigned using 2D homo-
nuclear correlation method COSY. The 13C signals
were assigned basing on the analysis of the 2D
heteronuclear correlation spectra HSQC and HMBC.
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This study was financially supported by the Russian
Scientific Foundation (Grant 18-73-10080) and per-
formed using the equipment of the Baikal Analytical
Center for Collective Usage, Siberian Branch of
Russian Academy of Sciences.
CONFLICT OF INTEREST
No conflict of interest was declared by authors.
REFERENCES
1. Gusarova, N.K., Volkov, P.A., Ivanova, N.I., Arbuzo-
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