Reaction of 9-bromoanthracene with red phosphorus in the system KOH?DMSO

Full text of DOI:10.1134/S1070428016070265

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 7, pp. 1059–1061. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © V.A. Kuimov, E.A. Matveeva, A.A. Telezhkin, S.F. Malysheva, N.K. Gusarova, B.A. Trofimov, 2016, published in Zhurnal
Organicheskoi Khimii, 2016, Vol. 52, No. 7, pp. 1064–1066.
SHORT
COMMUNICATIONS
Reaction of 9-Bromoanthracene with Red Phosphorus
in the System KOH‒DMSO
V. A. Kuimov, E. A. Matveeva, A. A. Telezhkin, S. F. Malysheva,
N. K. Gusarova, and B. A. Trofimov*
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
*e-mail: boris_trofimov@irioch.irk.ru
Received April 26, 2016
DOI: 10.1134/S1070428016070265
Organophosphorus compounds containing bulky
anthracene fragments attract interest as ligands for
metal complexes for various purposes [1–12], starting
materials for the design of luminescent materials
[12–16] (in particular, as components of molecular
switches [13]), and nanoparticle stabilizers (used, e.g.,
in therapy of oncological diseases) [17].
red phosphorus in the system KOH‒DMSO containing
a small amount of water we obtained anthracen-9-
ylphosphinic acid (2) in up to 10% yield (unop-
timized). Under these conditions, 30% of anthracene 3
and 20% of 9,10-dihydroanthracene (4) were also
formed (Scheme 1). The reaction mixture also
contained traces of anthracen-9-ol (according to the
GC/MS data).
Phosphorylation of anthracenes and their halogen
derivatives is usually accomplished with the aid of
phosphorus halides [5–7, 12, 18, 19], alkyl and aryl
phosphites [3, 17, 20–22], or hypophosphites [23]. For
example, anthracen-9-ylphosphinic acid was synthe-
sized in two steps including reaction of phosphorus
trihalide with anthrylmagnesium halide and subsequent
hydrolysis of anthryl(dihalo)phosphine [1]. Kalek and
Stawinski [23] described microwave-assisted synthesis
of anthracen-9-ylphosphinic acid from 9-bromoan-
thracene and anilinium phosphinite in the presence of
Pd2(dba)2·CHCl3‒Xantphos‒Et3N as catalytic system.
No phosphorylation of 1 was observed in the
absence of base, which confirms nucleophilic character
of the C‒P bond formation. In the first step, elemental
phosphorus in superbasic medium generates phos-
phorus-containing nucleophilic species, polyphosphide
(A) and polyphosphinite ions (B) [25, 26], which then
react with bromide 1 to give acid 2 (Scheme 2).
Polyphosphide ions are most likely to be involved
in concurrent one-electron transfer process with forma-
tion of unstable radical anion C which decomposes
into bromide ion and anthryl radical D. The latter is
capable of abstracting hydrogen from DMSO, yielding
neutral anthracene (3). The subsequent electron
transfer to molecule 3 from anion A or radical anion
C leads to the formation of the reduction product,
9,10-dihydroanthracene (4) (Scheme 3).
One of the most convenient methods for the forma-
tion of P–C bond and synthesis of organophosphorus
compounds is based on the direct reaction of elemental
phosphorus with electrophiles in the presence of strong
bases [24–31]. Herein, we report for the first time
phosphorylation of 9-bromoanthracene (1) with red
phosphorus. By heating (40‒60°C, 3 h) bromide 1 with
This mechanism is consistent with published data
for reactions of 9-bromoanthracene with sulfur and
Scheme 1.
Br
PH(O)OH
Pred, KOH (H2O), DMSO
+
+
1
2
3
4
1059

KUIMOV et al.
1060
Scheme 2.
O
O
HO–/H2O
HO–
HO–
1
–Br–
2
Pred
P
OH
P
P
–H2O
–
P– (A)
B
Scheme 3.
P– (A)
·
–
Br
2e/2H2O
·
Electron transfer
DMSO
Electron transfer
–2HO–
1
3
4
–Br–
C
D
oxygen nucleophiles in superbasic medium, where the
formation of anthracene was also detected [32–35].
The formation of 9,10-dihydroanthracene from anthra-
cene was observed in the strong reducing system
NiBr2–NaBH4 [36], under electrolysis conditions, or as
a result of electron transfer [37, 38].
containing compounds 3 and 4 and anthracen-9-ol at
a ratio of 60:39:1. Mass spectrum, m/z: 178 [M]+ (3);
180 [M]+ (4); 193 [M]+ (anthracen-9-ol).
The alkaline aqueous layer was acidified with
aqueous HCl to pH 4‒5, acid 2 was extracted into
chloroform (3 ×20 mL), the extract was dried over
CaCl2, the solvent was distilled off, and the residue
was dried under reduced pressure. Yield 0.09 g (10%).
The spectral parameters and analytical data for acid 2
Thus, we were the first to accomplish phosphoryla-
tion of 9-bromoanthracene with red phosphorus in
a superbasic system, which led to the formation of
anthracen-9-ylphosphinic acid and reduction products
(anthracene and 9,10-dihydroanthracene). Our results
1
(δP 13.5 ppm, JPH = 567 Hz; found, %: C 69.51;
H 4.49. C14H11O2P) were identical to those reported
in [1, 23].
make a contribution to the methodology of P‒Csp
2
bond formation by direct phosphorylation of weakly
electrophilic aromatic halogen derivatives with ele-
mental phosphorus and open the way to new organo-
phosphorus compounds with bulky organic radicals.
The latter are promising as ligands for the design of
catalytically active metal complexes, precursors to
medicines, luminophores, and building blocks for
organic synthesis.
The NMR spectra were recorded on a Bruker DPX-
400 spectrometer at 400.1 and 161.98 MHz for 1H and
31P, respectively, using CDCl3 as solvent and hexa-
methyldisiloxane (1H) or 85% H3PO4 (31P) as refer-
ence. Gas chromatographic/mass spectrometric anal-
yses were performed on an Agilent Technologies
6890N/5975C GC/MS system (HP-5MS column,
0.25 mm×30 m, film thickness 0.25 μm; carrier gas
helium; electron impact ionization, 70 eV). Elemental
analyses were obtained on a Flash EA 1112 Series
analyzer. Red phosphorus was commercial product
(KSAN SIA, China). All operations were carried out
under argon.
Reaction of red phosphorus with 9-bromoan-
thracene (1) in the system KOH‒DMSO (H2O).
A solution of 1.00 g (3.9 mmol) of compound 1 in
5 mL of DMSO was heated to 60°C, 0.4 g (13 mmol)
of red phosphorus, 1.25 g (19 mmol) of KOH·0.5H2O,
and 0.125 mL of water were added, and the mixture
was stirred for 3 h at 60°C under argon. The mixture
was cooled to room temperature and filtered from
unreacted phosphorus (0.1 g) through a Schott filter,
and the filtrate was diluted with water (20 mL) and
extracted with methylene chloride (3×20 mL). The
resulting emulsion was separated by centrifugation.
The organic layer was washed with 10% aqueous
potassium chloride (3×10 mL) and dried over Na2SO4,
the solvent was distilled off, and the residue was dried
under reduced pressure to obtain 0.337 g of a mixture
This work was performed using the facilities of the
Baikal Joint Analytical Center, Siberian Branch,
Russian Academy of Sciences.
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