Novel approach to metal-induced oxidative phosphorylation of aromatic compounds

Article abstract of DOI:10.1016/j.cattod.2016.06.001

We propose a new approach to the phosphorylation of benzenes bearing both electron withdrawing and electron donating substituents on the ring and some coumarins (coumarin, 6-methylcoumarin, 7-methylcoumarin) under the action of dialkyl H-phosphonate (RO)<

Full text of DOI:10.1016/j.cattod.2016.06.001

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Catalysis Today
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Novel approach to metal-induced oxidative phosphorylation of
aromatic compounds
M.N. Khrizanforov∗, S.O. Strekalova, K.V. Kholin, V.V. Khrizanforova, M.K. Kadirov,
T.V. Gryaznova, Y.H. Budnikova
A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, 8 Arbuzov Str., Kazan 420088, Russian
Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
We propose a new approach to the phosphorylation of benzenes bearing both electron withdrawing
and electron donating substituents on the ring and some coumarins (coumarin, 6-methylcoumarin, 7-
methylcoumarin) under the action of dialkyl H-phosphonate (RO)2P(O)H (R = Et, n-Bu, i-Pr), based on
catalytic oxidation of arene and H-phosphonate (1:1) mixture in electrochemically mild conditions (room
temperature, normal pressure) using the bimetallic catalyst system MnIIbpy/NiIIbpy (1%). This method
produces a dialkyl aryl phosphate with high yield (up to 70%) and 100% conversion of H-phosphonate.
© 2016 Elsevier B.V. All rights reserved.
Received 30 December 2015
Received in revised form 23 May 2016
Accepted 1 June 2016
Available online xxx
Keywords:
Phosphorylation
Oxidation
Electrosynthesis
catalyst
Metal
Complex
C
H functionalization
1. Introduction
by Masui [18] in 1979 and was later repeated by Kargin [19]
at a ratio (benzene: dialkyl H-phosphonate 5:1) in acetonitrile
Dialkyl aryl phosphonates are important as intermediates
in the synthesis of pesticides and bioactive compounds [1–4].
Several methods are recognized as being traditional for the syn-
thesis of dialkyl aryl phosphonates. The most common of them
involve the phosphorylation reaction of aryl halides [5–13]. It
has been described some examples of the radical phosphoryla-
tion of aromatic compounds by dialkyl H-phosphonate, including
naphthalene in the presence of tert-butyl peroxide [14], vari-
ous arenes in the presence of oxidants (NH4)2[Ce(NO3)6 [15] or
Na2S2O8 and AgNO3 [16], and Mn(II)/Co(II)/O2 [17], but the most
successful example is the Ishii phosphorylation of benzene by
dialkyl H-phosphonate [17]. However, it has a number of dis-
advantages, including an elevated reaction temperature but not
very high substrate conversion to monophosphorylation product,
being specifically 6% (25 ◦C) to 69% (60 ◦C) for benzene. The pos-
sibility of obtaining aryl phosphonates with yields of up to 59%
through the electrochemical oxidation of trialkyl phosphites in
the presence of benzene and its derivatives was first described
in the presence of background salt NaClO4. Gallardo proposed
the electrochemical phosphorylation of benzene nitro derivatives
with phosphorus(III) compounds, including dialkyl H-phosphonate
under oxidizing conditions [20]; however, his approach does not
work for non-substituted benzene because the key step of the
process is nucleophilic addition of H-phosphonate to the aro-
matic ring (SNAr mechanism) followed by ␴-H adduct oxidation.
More recently in 2013 Cheng et al. [21] developed a phos-
phorylation method of aromatic substrates, benzene derivatives
containing electron-deficient directing groups catalyzed by system
AgI/K2S2O8, but the method did not prove suitable for benzene. A
novel efficient Pd-catalyzed cross-coupling of triarylbismuths with
a variety of P(O) H compounds has been developed by Yufen Zhao
and coll. [22]. This method provides a general tool for the prepa-
ration of various valuable arylphosphonates, arylphosphinates,
and arylphosphine oxides, but is unsuitable for direct aromatic
C
H phosphonation. Copper-catalyzed phosphorylation of termi-
nal alkynes in the presence of diphenylphosphine oxide added
dropwise to the reaction mixture is one of new examples of P-C
cross-coupling reactions [23].
The preparation of aryl phosphonate through the direct phos-
phorylation of C Н bond of aromatic substrates remains one of the
∗
Corresponding author.
E-mail address: khrizanforov@gmail.com (M.N. Khrizanforov).
http://dx.doi.org/10.1016/j.cattod.2016.06.001
0920-5861/© 2016 Elsevier B.V. All rights reserved.
Please cite this article in press as: M.N. Khrizanforov, et al., Novel approach to metal-induced oxidative phosphorylation of aromatic
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Table 1
2
most important approaches because it corresponds to the princi-
ples of green chemistry, namely atom economy, single-step, low
in waste, etc. The desired catalytic conditions in this context are
particularly attractive, given the fact that the catalytic reactions
of aromatic compounds phosphorylation are limited. Perhaps ben-
zene in this row is one of the most difficult substrates, given that its
structure has no favorable C H substitution factors, i.e., functional
groups, activating bonds or directing functionalization. Typically,
if it is possible to select conditions for the phosphorylation of ben-
zene, its derivatives give even higher yields [17–19].
3-Phosphonated coumarins have been shown to exhibit their
cytotoxicity on some human leukemia cell lines as well as high
alkylating activity [24–26] as was heretofore usually obtained
through Arbuzov [27–30] or Knoevenagel [31–33] reactions. Gen-
erally these methods give byproducts, are often based on the
multi-stage consecutive reactions and do not correspond to the
principles of atom economy, and hence have a low efficiency. As
far as is known, until recently only a few reports from the Zhang
[34], Wu [35] and Qu [36] research groups described the phos-
phorylation of coumarins through radical reaction, which required
excessive amounts of Mn(OAc)3 (3 eqv.) and an aliphatic acid as
a solvent [34] or salts of expensive metals such as silver [36] and
palladium [35].
Electrochemical phosphorylation of arenes by dialkyl H-phosphonates (at the ratio
of 1:1). Conditions: room temperature, Q = 2 F per mol dialkyl H-phosphonate, gal-
vanostatic mode when using (1%) [MnCl2bpy/Ni(BF4)2bpy], with isolated yields.
bpy: 2,2ꢀ-bipyridine.
Product
Yield (%)
Electrosynthesis immediately
after the mixing of substrates
Electrosynthesis 1 day after
mixing of substrates
1
2
3
4
5
6
7
8
30
29
30
30
37
31
30
36
35
25
37
29
50
46
48
55
70
61
54
68
58
50
71
60
68
56
71
9
10
11
12
[13:14] = [1:2] 25
[15:16] = [1:1] 30
[17:18] = [1:4] 30
Table 2
Potentials and currents of the first oxidation peaks of catalysts used for the arenes
phosphorylation reaction at room temperature.
None of the known methods described above allows one to
obtain an arene phosphorylation product with high yield and con-
version at room temperature in a single stage. In that regard,
electrochemical catalytic reactions of aromatic compounds direct
phosphorylation [37–42] are particularly attractive. We assume
that it would be possible to realize the phosphorylation of ben-
zene and coumarin by taking advantage of electrochemical metal
complex catalysis [43–47].
Complex
Ep (V)
Ni(BF4)2bpy
MnCl2bpy
1.90 (35 ␮A)
1.14 (32 ␮A)
material of the auxiliary electrode was platinum, the reference
electrode was Ag/AgCl equipped with a bridge of a carbon slate-
pencil, and a gold wire 0.5 mm in diameter served as a working
electrode. The measurements were carried out on an apparatus
program complex including an analog electrochemical system with
a potentiostat and a PWR-3 programmer, an ELEXSYS E500 ESR
spectrometer of the X-range, and an E14-440 analog-to-digital and
digital-to-analog modulus (L-Card), a fourth-generation computer,
and a unique three-electrode helical cell [48,49]. ESR spectra were
simulated using the WinSim 0.96 program (developed by NIEHS).
2. Materials and methods
2.1. Cyclic voltammetry
Cyclic voltammograms were recorded with a BASi Epsilon
E2P (USA) potentiostat. The device comprises a measuring unit,
PC DellOptiplex 320 with the Epsilon-EC-USB-V200 software. As
background electrolytes, tetrabutylammonium tetrafluoroborate
(C4H8)4NBF4 was used. The working electrode was a stationary
disc glassy-carbon electrode (the surface area of 6 mm2). Ag/AgCl
(0.01 М KCl) was used as a reference electrode and a Pt wire as
counter electrode. The reference electrode was connected with the
cell solution by a modified Luggin capillary filled with the sup-
porting electrolyte solution (0.1 M Bu4NBF4 in CH3CN). Thus, the
reference electrode assembly had two compartments, each termi-
nated with an ultra-fine glass frit to separate the AgCl from the
analyte.
A platinum wire was used as an auxiliary electrode. The scan
rate was 100 mV s−1. The measurements were performed in a
temperature-controlled electrochemical cell (volume from 1 mL to
5 mL) in an inert gas atmosphere (N2). Between measurements or
prior to a registration of a voltammetry wave, the solution was
actively stirred with a magnetic stirrer in the atmosphere of con-
stant inflow of an inert gas that was run through a dehydrating
system, and then through a nickel-based purification system BI-
GAScleaner (manufactured by OOO Modern Laboratory Equipment,
Novosibirsk) to remove trace quantities of oxygen.
2.3. Preparative electrochemical syntheses
All reactions were carried out under dry argon atmosphere. The
preparative electrolyzes were performed using a direct current
source B5-49 in a three-electrode cell with 40 mL volume with a
separation of the anode and cathode compartments. The potential
value of the working electrode was recorded using a direct current
voltmeter V7-27 in relation to the Ag/AgCl (0.01 M, NaCl) reference
electrode that had two sections separated with Vycor, the second
of them containing a saturated solution of the background salt in
CH3CN. The surface area of the working platinum (Pt) U-shaped
electrode amounted to 48.00 cm2. A ceramic plate with a pore size
of 10 ␮m was used as a membrane. During the preparative synthe-
sis, the electrolyte was continuously stirred using a magnetic stirrer
with a continuous inflow of an inert gas that was run through a
purification system to remove oxygen and other impurity gases. A
platinum grid served as a cathode, and the catholyte was a satu-
rated solution of Et4NBF4 and PyHBF4 supporting electrolyte in the
corresponding solvent.
2.2. ESR experiments
2.4. NMR experiments
Oxygen was removed from liquid samples by three cycles of
“freezing in liquid nitrogen – evacuation – thawing” and after the
last cycle the electrolysis cell was filled with gaseous helium. The
NMR spectra were recorded with multi-nuclear spectrome-
ter Bruker AVANCE-400 (400.1 MHz (1H), 100.6 MHz (13C) and
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Electrolysis was carried out in an electrochemical cell with separa-
tion of anode and cathode compartments at ambient temperature
under argon atmosphere at the potential of a working electrode
1.0 V. The amounts of electricity passed through the electrolyte
were 2 F per one mole of H-phosphonate (104 mA × h−1). After com-
pleting the electrolysis, the solution was filtrated, and the solvent
was distilled under vacuum. The crude product was purified by sil-
ica gel column chromatography to give the desired product 3 using
ethylacetate/petroleum ether (1:5–2:1) as eluent. The yields are
given in Table 1.
295 K
255 K
215 K
175 K
135 K
2.7.1.1. Diethyl phenylphosphonate (1). Colorless oil 31P NMR
(162 MHz, CDCl3) 18.3; 1H NMR (400 MHz, CDCl3) 7.82–7.73 (m,
2H), 7.55–7.47 (m, 1H), 7.43–7.38 (m, 2H), 4.16–3.87 (m, 4H), 1.31
(t, JH-H = 7.0 Hz, 6H). 13C NMR (100 MHz, CDCl3) 132.3, 131.5, 128.5,
128.1, 62.2, 16.3. IR (liq, ꢁ; cm−1): 2995, 2944 ( CH3), 1611, 1504
(Ar ), 1453 (P C), 1241 (P O), 1090 (P O).EIMS, m/z: 214.33 [M]+;
Anal. calc. (%):C, 56.07; H, 7.06; O, 22.41; P, 14.46 for C10H15O3P,
Found: C, 56.03; H, 7.03; P, 14.40. The spectroscopic data for 1
matched that reported in the literature [52].
0
2000
4000
6000
8000
Magnetic field /G
Fig. 1. Temperature dependence of the ESR spectrum of the MnCl2bpy powder.
162.0 MHz (31P)). Chemical shifts are given in parts per million rel-
ative to SiMe4 (1H, internal solvent) and 85% H3PO4 (
31P, external).
2.7.1.2. Diisopropyl phenylphosphonate (2). Colorless oil, 31P NMR
(162 MHz, CDCl3) 16.6; 1H NMR (400 MHz, CDCl3) 7.84–7.75 (m,
2H), 7.55–7.47 (m, 1H), 7.44–7.40 (m, 2H), 4.74–4.62 (m, 2H), 1.37
(d, JH-H = 6.6 Hz, 6H), 1.22 (d, JH-H = 6.6 Hz, 6H); 13C NMR (100 MHz,
CDCl3) 132.3, 131.5, 130.5, 128.3, 70.7, 24.1-23.7. IR (liq, ꢁ; cm−1):
2987, 2942 (-CH3), 1611, 1515 (Ar ), 1452 (P C), 1247 (P O), 1087
(P O), EIMS, m/z: 242.26 [M]+; Anal. calc. (%):C, 59.50; H, 7.91; O,
19.81; P, 12.79 for C12H13O3P, Found: C, 59.49; H, 7.85; P, 12.75.
The spectroscopic data for 2 matched that reported in the literature
[52].
2.5. Reagents and research subjects
CH3CN (“extra pure”), dibutyl phosphite, diisopropyl phosphite
(98%), diethyl phosphite (98%) (by Acrosorganics) were used with-
out a preliminary purification.
Et4NBF4 was obtained by mixing 30–35% water solution of
tetraethylammonium hydroxide, Et4NOH and HBF4 acid to a neu-
tral indicator reaction. In the course of the reaction, a white crystal
precipitation is deposited, which is filtered and dehydrated. The
obtained powder salts were recrystallized from ethyl ester and
were dried for 2–3 days in a vacuum at 55 ◦C.
2.7.1.3. Dibutyl phenylphosphonate (3). Colorless oil, 31P NMR
(162 MHz, CDCl3) 19.4; 1H NMR (400 MHz, CDCl3) 7.83-7.72 (m,
2H), 7.55–7.38 (m, 3H), 4.11–3.92 (m, 4H), 1.68–1.60 (m, 4H),
1.44–1.31 (m, 4H), 0.91 (t, JH-H = 7.3 Hz, 6H). 13C NMR (100 MHz,
CDCl3) 132.3, 131.6, 128.4, 128.3, 65.7, 32.4, 18.7, 13.3. IR (liq, ꢁ;
cm−1): 2988, 2941 ( CH3), 1612, 1513 (Ar ), 1449 (P C), 1245
(P O), 1086 (P O), EIMS, m/z: 270.31 [M]+; Anal. calc. (%):C, 62.21;
H, 8.58; O, 17.76; P, 11.46 for C14H23O3P, Found: C, 62.15; H, 8.50;
P, 11.41. The spectroscopic data for 3 matched that reported in the
literature [52].
Nitrobenzene (99 + %) (by Acros Organics) was used without a
preliminary purification.
2H-chromen-2-one (99%), N,N-Dimethylaniline (ReagentPlus,
99%), Benzonitrile (99 + %), 7-methyl-2H-chromen-2-one (98%), 6-
methyl-2H-chromen-2-one (99%) benzene (CHROMASOLV® Plus,
≥99.9%) (by Sigma Aldrich) were used without a preliminary purifi-
cation.
2.6. Synthesis of the metal complexes
2.6.1. Synthesis of [Mn(ꢀ-Cl)2(bpy)]n
2.7.1.4. Diethyl 2-oxo-2H-chromen-3-ylphosphonate (4). White
solid; mp = 65–66 ◦C. 31P NMR (162 MHz, CDCl3) 10.37. 1H NMR
(400 MHz, CDCl3): 8.53 (d, 3JPH = 17.2 Hz, 1H, C4 H), 7.66–7.60 (m,
2H, ArH), 7.37–7.33 (m, 2H, ArH), 4.34–4.22 (m, 4H, 2CH2), 1.37
(t, J = 7.1 Hz, 6H, 2CH3). 13C NMR (100.6 MHz, CDCl3): 158.3 (d,
JP-C = 22.7 Hz), 155.3, 153.5 (d, JP-C = 6.4 Hz), 134.4, 129.5, 125.1,
To an ethanol solution of MnCl2&903;4H2O (18.3 mmol)
(100 mL), an ethanol solution (50 mL) of bpy ligand (18.3 mmol)
was added under stirring. The resulting solution was stirred for
1 h, then filtered and left to evaporate at room temperature.
After several days, air-stable, yellow crystals of this complex were
obtained. Yield: 75%. Anal. calc. (%): C, 42.50; H, 2.83; N, 9.92.
(C10H8Cl2MnN2) Found: C, 42.54; H, 2.89; N, 9.73%. The spectro-
scopic data for [Mn(␮-Cl)2(bpy)]n matched that reported in the
literature [50].
1
118.0 (d, JP-C = 14.1 Hz), 117.9 (d, JP-C = 196.9 Hz), 116.9, 63.5 (d,
JP-C = 9.2 Hz), 16.5 (d, JP-C = 10.1 Hz). EIMS, m/z: 282.84 [M]+; IR
(KBr, ꢁ; cm−1): 2983, 2920, 2875 ( CH3, CH2 ), 1743 (C O),
1610, 1562 (Ar ), 1430 (P C), 1248 (P O), 1055 (P-O). Anal. calc.
(%): C, 55.32; H, 5.36; O, 28.34; P, 10.97, C13H15O5P, Found: C,
55.31; H, 5.33; P, 10.92. The spectroscopic data for 4 matched that
reported in the literature [34].
2.6.2. Synthesis of Ni(BF4)2bpy
Similarly like the synthesis of [Mn(␮-Cl)2(bpy)]n, but instead
MnCl2&903;4H2O used 18.3 mmol Ni(BF4)2&903;3H2O. (75% iso-
lated yield of Ni(BF4)2bpy). The spectroscopic data for Ni(BF4)2bpy
matched that reported in the literature [51].
2.7.1.5. Diethyl 7-methyl-2-oxo-2H-chromen-3-ylphosphonate (5).
Yellow solid; mp = 62–64 ◦C; 31P NMR(162 MHz, CDCl3) 10.9. 1H
NMR (400 MHz, CDCl3): 8.40 (s, 1H, C4 H), 7.39 (d, J = 7.5 Hz, 1H,
ArH), 7.06 (d, J = 7.4 Hz, 2H, ArH), 4.19 (m, 4H, 2CH2), 2.40 (s, 3H, 7-
CH3), 1.30 (s, 6H, 2 CH3). 13C NMR (100.6 MHz, CDCl3): 158.9, 155.6,
2.7. Phosphorylation of aromatic compounds
1
2.7.1. General procedure
153.7, 146.4, 129.3,126.4, 117.1, 115.8, 106.6 (d, JP-C = 197.4 Hz),
A solution for electrolysis was prepared by mixing 0.012 mmol
[Mn(␮-Cl)2(bpy)]n, 0.012 mmol Ni(BF4)2bpy, 1.2 mmol arene,
1.2 mmol H-phosphonate and 2 mmol of Et4NBF4 in CH3CN (40 mL).
63.5, 22.3, 16.6. EIMS, m/z: 296.47 [M]+. IR (KBr, ꢁ; sm−1): 3061,
2966, 2861 ( CH3, CH2 ), 1721 (C O), 1210 (P O), 1039 (P O).
Anal. calc.: C, 56.76; H, 5.78; O, 27.00; P, 10.46 for C14H17O5P.
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Scheme 1. The phosphorylated arenes obtained in electrochemical condition.
Found: C, 56.67; H, 5.71; P, 10.42 The spectroscopic data for 5
matched that reported in the literature [34].
7.32–7.28 (m, 2H), 4.87–4.79 (m, 2H), 1.34 (dd, JP-H = 12.9 Hz,
JH-H = 6.0 Hz, 12H). 13C NMR (100 MHz, CDCl3) 158.1 (d, JP-
C = 22.9 Hz), 155.2, 152.9 (d, JP-C = 10.7 Hz), 134.0, 129.3, 124.8,
119.8, 118.0, 116.8, 72.2, 24.0 (d, JP-C = 6.8 Hz), 23.8. IR (KBr, ꢁ;
cm−1): 2991, 2936 ( CH3), 1741 (C O), 1611, 1595 (Ar ), 1450
(P C), 1248 (P O), 1105 (P O). EIMS, m/z: 310,36 [M]+. Anal.calc.
(%): C, 58.06; H, 6.17; O, 25.78; P, 9.98 for C15H19O5P. Found: C,
58.01; H, 6.13; P, 9.89. The spectroscopic data for 7 matched that
reported in the literature [36].
2.7.1.6. Diethyl 6-methyl-2-oxo-2H-chromen-3-ylphosphonate (6).
Yellow solid; mp = 74–76 ◦C; 31P NMR (162 MHz, CDCl3) 11.4. 1H
NMR (400 MHz, CDCl3): 8.40 (d, J = 17.1 Hz, 1H, 4-H), 7.38 (d,
J = 8.5 Hz, 1H, ArH), 7.30 (s, 1H, ArH), 7.17 (d, J = 8.5 Hz, 1H, ArH),
4.23–4.17 (m, 4H, 2CH2), 2.35 (s, 3H, 6-CH3), 1.31 (t, J = 7.4 Hz, 6H,
2CH3). 13C NMR (100.6 MHz, CDCl3): 159.0, 158.9, 153.7, 153.6,
135.6, 135.0, 129.2, 117.9, 117.8, 116.8, 63.6, 20.9, 16.6. EIMS, m/z:
296.44 [M]+. IR (KBr, ꢁ; cm−1): 3057, 2963, 2857 ( CH3, CH2 ),
1719 (C O), 1211 (P O), 1039 (P O). Anal. calc.: C, 56.76; H, 5.78;
O, 27.00; P, 10.46 for C14H17O5P. Found: C, 56.64; H, 5.73; P, 10.41.
The spectroscopic data for 6 matched that reported in the literature
[34].
2.7.1.8. Diisopropyl 7-methyl-2-oxo-2H-chromen-3-ylphosphonate
(8). Colorless vis-cous oil.; 31P NMR (162 MHz, CDCl3) 9.1, 1H NMR
(400 MHz, CDCl3, ı) 8.37 (d, JP-H = 6.8 Hz, 1H), 7.42 (d, JH-H = 8.7 Hz,
1H), 6.82 (dd, JH-H = 8.7 Hz, 1H), 6.74 (d, 1H), 4.80–4.72 (m, 2H),
2.40 (s, 3H), 1.33 (d, 6H), 1.26 (d, 6H). 13C NMR (100 MHz, CDCl3, ı):
164.7, 158.4 157.4, 152.9, 130.4, 113.2, 111.7, 100.5, 71.9, 55.9, 24.0,
23.8. IR (KBr, ꢁ; cm−1): 2991, 2981 ( CH3), 1738 (C O), 1610, 1503
(Ar ), 1377 (P C), 1250 (P O). EIMS, m/z: 324,61 [M]+. Anal.calc.
2.7.1.7. Diisopropyl 2-oxo-2H-chromen-3-ylphosphonate (7). White
solid, mp = 95–96 ◦C; 31P NMR (162 MHz, CDCl3) 8.2, 1H NMR
(400 MHz, CDCl3) 8.49 (d,NJP-H = 6.9 Hz, 1H), 7.63–7.54 (m, 2H),
mI=1/2
2800
3000
3200
3400
3600
3800
4000
2800
3000
3200
3400
3600
3800
4000
Magnetic field / G
Magnetic field / G
Fig. 2. ESR spectra: 4 × 10−6 mol MnCl2bpy in 5 mL of CH3CN (left), mixture [(4 × 10−6 mol MnCl2bpy) + (HP(O)(OEt)2)] in 5 mL of CH3CN (right) at 25 ◦C.
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(%): C, 59.26; H, 6.53; O, 24.67; P, 9.55 for C16H21O5P. Found: C,
59.27; H, 6.51; P, 9.31
mI=1/2
2.7.1.9. Diisopropyl 6-methyl-2-oxo-2H-chromen-3-ylphosphonate
(9). White solid, mp = 70–73 ◦C. 31P NMR (162 MHz, CDCl3, ı) 7.9,
1H NMR (400 MHz, CDCl3, ı) 8.41 (d, JP-H = 6.9 Hz, 1H), 7.38 (dd,
JH-H = 8.5 Hz, 1H), 7.30 (d, 1H), 7.18 (d, JH-H = 8.5 Hz, 1H), 4.85–4.77
(m, 2H), 2.37 (s, 3H), 1.36 (d, JH-H = 6.2 Hz, 6H), 1.28 (d, JH-H = 6.2 Hz,
6H). 13C NMR (100 MHz,CDCl3, ı) 158.3, 153.3, 152.9, 135.0, 134.5,
128.9, 119.6, 117.7, 116.4, 72.2, 24.0, 23.8, 20.6. IR (KBr, ꢁ; cm−1):
1732 (C O), 1627, 1510 (Ar ), 1387 (P C), 1251 (P O). EIMS, m/z:
324,39 [M]+. Anal.calc. (%): C, 59.26; H, 6.53; O, 24.67; P, 9.55 for
2800
3000
3200
3400
3600
3800
4000
C16H21O5P. Found: C, 59.27; H, 6.48; P, 9.51. The spectroscopic data
for 9 matched that reported in the literature [36].
Magnetic field / G
Fig. 3. EPR spectrum of the mixture [(4 × 10−6 mol MnCl2bpy) + (HP(O)(OEt)2)
2.7.1.10. Dibutyl 2-oxo-2H-chromen-3-ylphosphonate (10). Color-
less vis-cous oil. 31P NMR (162 MHz, CDCl3, ı) 11.2, 1H NMR
(400 MHz, CDCl3, ı) 8.52 (d, JP-H = 6.9 Hz, 1H), 7.67–7.55 (m, 2H),
7.36–7.30 (m, 2H), 4.24–4.13(m, 4H), 1.71–1.66 (m, 4H), 1.45–1.36
(m, 4H), 0.91 (t, JH-H = 7.4 Hz, 6H). 13C NMR (100 MHz, CDCl3, ı)
158.1, 155.2, 153.4, 134.1, 129.3, 124.8, 118.8, 117.9, 116.8, 67.1,
32.4, 18.6, 13.5. IR (liq, ꢁ; cm−1): 2960, 2932, 2873 ( CH3, CH2),
1732 (C O), 1610, 1564 (Ar ), 1447 (P C), 1250 (P O). EIMS, m/z:
338,70 [M]+. Anal.calc. (%): C, 60.35; H, 6.85; O, 23.64; P, 9.15 for
C17H23O5P. Found: C, 60.39; H, 6.82; P, 9.09. The spectroscopic data
for 10 matched that reported in the literature [36].
+ Ni(BF4)2bpy] in 5 mL of CH3CN.
Time
+ 1.0 V
2.7.1.11. Dibutyl
7-methyl-2-oxo-2H-chromen-3-ylphosphonate
(11). Colorless viscous oil. 31P NMR (162 MHz, CDCl3, ı) 11.0, 1H
NMR (400 MHz, CDCl3, ı) 8.54 (d, JP-H = 6.8 Hz, 1H), 7.68–7.55 (m,
1H), 7.20–7.03 (m, 2H), 4.24–4.17(m, 4H), 2.40 (s, 3H), 1.74-1.68
(m, 4H), 1.45–1.36 (m, 4H), 0.91 (t, JH-H = 7.4 Hz, 6H). 13C NMR
(100 MHz, CDCl3, ı) 161.7, 156.9, 153,1, 139.1, 129.9, 124.8, 118.8,
117.9, 116.8, 67.1, 31.7, 21.3, 18.3, 13.9. IR (liq, ␯; cm−1): 2960,
2932, 2873 ( CH3, CH2), 1732 (C O), 1610, 1564 (Ar ), 1447
(P C), 1250 (P O). EIMS, m/z: 352,70 [M]+. Anal.calc. (%): C, 61.36;
H, 7.15; O, 22.70; P, 8.79 for C18H25O5P. Found: C, 61.37; H, 7.13;
P, 8.71.
2800
3000
3200
3400
3600
3800
4000
Magnetic field / G
Fig. 4. EPR spectrum of the mixture 4 × 10−6 mol [MnCl2bpy + Ni(BF4)2bpy
+ HP(O)(OEt)2 + Bu4NBF4] in 5 mL CH3CN during electrochemical oxidation (1.0 V).
(
CN), 1601, 1499 (Ar ), 1444 (P-C), 1254 (P O). EIMS, m/z: 239,10
2.7.1.12. Dibutyl
6-methyl-2-oxo-2H-chromen-3-ylphosphonate
[M]+. Anal.calc. (%): C, 55.23; H, 5.90; N, 5.86; O, 20.07; P, 12.95 for
C11H14NO3P. Found: C, 55.28; H, 5.85; P, 12.90. The spectroscopic
data for 14 matched that reported in the literature [53].
(12). Colorless viscous oil. 31P NMR (162 MHz, CDCl3, ı) 12.1,1H
NMR (400 MHz, CDCl3, ı) 8.73 (d, JP-H = 6.8 Hz, 1H), 7.49–7.35 (m,
3H), 4.21–4.11 (m, 4H), 1.71–1.66 (m, 4H), 1.8–1.51 (m, 8H), 0.95
(t, JH-H = 7.4 Hz, 6H). 13C NMR (100 MHz, CDCl3, ı) 161.1, 156.7,
151,2, 135.0, 129.9, 124.8, 118.8, 117.9, 116.8, 67.1, 31.7, 22.1,
18.3, 13.7. IR (liq, ꢁ; cm−1): 2981, 2961 ( CH3, CH2), 1735 (C O),
1618, 1530 (Ar ), 1444 (P C), 1254 (P O). EIMS, m/z: 352,40 [M]+.
Anal.calc. (%): C, 61.36; H, 7.15; O, 22.70; P, 8.79 for C18H25O5P.
Found: C, 61.39; H, 7.09; P, 8.73.
2.7.1.15. Diethyl 3-(dimethylamino)phenylphosphonate (15). Yel-
low solid; mp = 55–58 ◦C; 31P NMR (162 MHz, CDCl3, ı) 19.2,1H
NMR (400 MHz, CDCl3, ı) 7.59–7.50 (m, 2H), 7.35–7.29 (m, 3H),
4.21–4.01 (m, 4H), 2.98 (s, 6H), 1.27 (t, JH-H = 7.1 Hz, 6H). 13C NMR
(100 MHz, CDCl3, ı) 138.2 (d, J = 14.9 Hz), 133,3, 132.3, 129.2, 128.4,
128.0, 62.0, 41.1, 16.1. IR (KBr, ꢁ; cm−1): 3021( NMe2), 2981, 2961
(
CH3, CH2), 1613, 1532 (Ar ), 1444 (P C), 1254 (P O). EIMS,
2.7.1.13. Diethyl 3-cyanophenylphosphonate (13). Colorless viscous
oil. 31P NMR (162 MHz, CDCl3, ı) 17.1,1H NMR (400 MHz, CDCl3, ı)
8.73-8.38 (m, 2H), 8.17–8.11 (m, 1H), 7.74–7.68 (m, 1H), 4.27–4.11
(m, 4H), 1.36 (t, JH-H = 7.4 Hz, 6H). 13C NMR (100 MHz, CDCl3, ı)
148.1, 137.4, 131,2, 129.7, 126.9, 124.8, 62.8, 42.1, 16.7. IR (liq, ꢁ;
cm−1): 2981, 2961 ( CH3, CH2); 2235 ( CN), 1610, 1504 (Ar ),
1444 (P-C), 1243 (P O). EIMS, m/z: 239,15 [M]+, 262.06 [M + Na]+.
Anal.calc. (%): C, 55.23; H, 5.90; N, 5.86; O, 20.07; P, 12.95 for
C11H14NO3P. Found: C, 55.27; H, 5.79; P, 12.89.
m/z: 257,42 [M]+. Anal.calc. (%): C, 56.02; H, 7.84; N, 5.44; O, 18.66;
P, 12.04 for C12H20NO3P. Found: C, 56.12; H, 7.79; P, 11.96.
2.7.1.16. Diethyl 4-(dimethylamino)phenylphosphonate (16). Yel-
low solid; mp = 124–127 ◦C; 31P NMR (162 MHz, CDCl3, ı) 17.3,
1H NMR (400 MHz, CDCl3, ı) 7.73–7.65 (m, 2H), 7.28–7.23 (m,
2H), 4.15–4.01 (m, 4H), 3.02 (s, 6H), 1.29 (t, JH-H = 7.2 Hz, 6H). 13C
NMR (100 MHz, CDCl3, ı) 144.1, 132.8, 130.9, 125.8, 62.7, 41.3,
16.3. IR (KBr, ꢁ; cm−1): 3025 ( NMe2), 2984, 2962 ( CH3, CH2),
1618, 1532 (Ar ), 1444 (P C), 1254 (P O). EIMS, m/z: 257,33 [M]+.
Anal.calc. (%): C, 56.02; H, 7.84; N, 5.44; O, 18.66; P, 12.04 for
C12H20NO3P. Found: C, 56.13; H, 7.78; P, 11.98.
2.7.1.14. Diethyl 4-cyanophenylphosphonate (14). White solid;
mp = 31–33 ◦C; 31P NMR (162 MHz, CDCl3, ı) 15.5, 31P NMR
(162 MHz, CD3CN, ı) 17.1, 1H NMR (400 MHz, CDCl3, ı) 7.92
(dd,JP-H = 13.4 Hz, 2H), 7.78–7.72 (m, 2H), 4.23–4.07 (m, 4H), 1.34 (t,
JH-H = 7.3 Hz, 6H). 13C NMR (100 MHz, CDCl3, ı) 146.1, 134.4, 126,2,
117.5, 62.4, 18.3. IR (KBr, ꢁ; cm−1): 2981, 2961 ( CH3, CH2), 2220
2.7.1.17. Diethyl 3-nitrophenylphosphonate (17). Yellow viscous
oil. 31P NMR (162 MHz, CDCl3, ı) 14.5, 31P NMR (162 MHz, CD3CN,
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Scheme 2. Catalytic cycle scheme of metal-induced phosphorylation of benzene under oxidative conditions.
Table 3
(1:1) and a room temperature of reaction that has not previously
been able to obtain aryl phosphonate with a good yield. The testing
of selected catalytic systems was performed with the use of dialkyl
H-phosphonates (Scheme 1), which are commercially available, rel-
atively inexpensive and stable phosphorylating reagents.
Catalytic current growth of first oxidation peaks of catalyst systems used for the
phosphorylation reaction at room temperature [Mbpy] = 5 × 10−4 M.
System
Ratio
icat/ip
MnCl2bpy: HP(O)(OEt)2
Ni(BF4)2bpy: HP(O)(OEt)2
Ni(BF4)2bpy: MnCl2bpy:HP(O)(OEt)2
1:6
1:6
1:1:6
2.13
1.30
2.50
Phosphorylated derivatives of benzene bearing both electron
withdrawing and electron donating substituents on the ring are
of particular interest due to their practically useful qualities found
in a wide range of properties. Therefore, direct phosphorylation
reaction of these derivatives are the subject of certain studies. It
is important to note, that only arenes bearing electron-donating
groups were mainly suitable for dehydrogenative cross-coupling
reactions with dialkyl phosphites in majority literature exam-
ples [16,17]. The reports on phosphonation of arenes bearing
strongly electron-deficient groups such as cyano and nitro groups
are few [21,53,54]. We investigated the scope of the reaction
by employing different derivatives of benzene bearing both elec-
tron withdrawing and electron donating substituents on the
ring and H-phosphonates, and the results were summarized in
Table 1.
It has been found that the combined electrolysis of alkyl H-
phosphonate and arene in the presence of catalyst comprising a
mixture of MnII/NiII complexes with a total content of 1% with
respect to the coupling partners (1:1) provides under oxidizing con-
ditions of phosphorylation of benzene, substituted benzenes and
coumarins product yields up to 68–71% in some cases (Table 1).
Interestingly, the highest yields can be obtained after reaction mix-
ture is storing for a period of time before electrolysis, which is
necessary for the formation of metal phosphonates [42].
ı) 16.1,1H NMR (400 MHz, CDCl3, ı) 8.66–8.60 (m, 1H), 8.40–8.37
(m, 1H), 8.18–8.11 (m, 1H), 7.71–7.66 (m, 1H), 4.24–4.12 (m, 4H),
1.35 (t, JH-H = 7.3 Hz, 6H). 13C NMR (100 MHz, CDCl3, ı) 148.1, 137.3,
131,2, 129.8, 126.9–126.7, 63.1, 16.3. IR (liq, ꢁ; cm−1): 2983, 2966
(
CH3, CH2), 1527 ( NO2), 1444 (P C), 1352, 1342 (C NO2) 1270
(P O). EIMS, m/z: 259,09 [M]+. Anal.calc. (%): C, 46.34; H, 5.44; N,
5.40; O, 30.86; P, 11.95 for C10H14NO5P. Found: C, 46.39; H, 5.39; P,
11.73. The spectroscopic data for 17 matched that reported in the
literature [54].
2.7.1.18. Diethyl 4-nitrophenylphosphonate (18). Colorless viscous
oil. 31P NMR (162 MHz, CDCl3, ı) 13.2, 1H NMR (400 MHz, CDCl3,
ı) 8.33 (dd, J = 6.9 Hz, 2H), 7.97 (dd, J = 12.7 Hz, 2H), 4.21–4.11 (m,
4H), 1.71–1.66 (m, 4H), 1.37 (t, J = 7.2 Hz, 6H). 13C NMR (100 MHz,
CDCl3, ı) 163.0, 134.6, 123.9, 117.3, 64.5, 17.3 (d, J = 6.2 Hz). IR (liq,
ꢁ; cm−1): 2980, 2961 ( CH3, CH2), 1520 ( NO2), 1441 (P C),
1245 (P O), 1040–1010. EIMS, m/z: 259,40 [M]+. Anal.calc. (%): C,
46.34; H, 5.44; N, 5.40; O, 30.86; P, 11.95 for C10H14NO5P. Found:
C, 46.41; H, 5.38; P, 11.75. The spectroscopic data for 18 matched
that reported in the literature [54].
It is important to note that 100% conversion of the dialkyl H-
phosphonate achieved in these syntheses, and after passing 2 F
electricity it was absent in the reaction mixture. Various electron-
poor or electron-rich aromatic substrates were effective substrates
to afford the coupling products in good yields (Table 1).
In contrast to the conditions of the phosphorylation coumarin
reaction according to the Wu method [35], which involve the use
of (10%) PdIIbpy and oxidant K2S2O8 (3 eqv.), under our conditions,
arylphosphonate was obtained in the presence of a bimetallic cat-
3. Results and discussion
3.1. Preparative electrosynthesis
We chose metal complexes in the oxidation state (II) as cata-
lyst systems for the electrochemical phosphorylation of benzene,
which could be electrochemically oxidized to M(III): Mn(II)bpy and
Ni(II)bpy. A distinctive feature of the process is its selected condi-
tions (Table 1), an equimolar ratio of arenes: dialkyl H-phosphonate
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7
Fig. 5. Cyclic voltammogramms of complexes oxidation (5 × 10−4 М) in the presence of increasing amounts of HP(O)(OEt)2: (a) MnCl2bpy (0, 1:1, 1:2, 1:3, 1:6, 1:24, 1:48,
1:72, 1:96, 1:120, 1:144, 1:168), (b) Ni(BF4)2bpy (5 × 10−4 М) (1:6, 1:12, 1:18, 1:24, 1:36, 1:72). (c) Mixture bpyNi(BF4)2 + bpyMnCl2 (1:1, 1:6, 1:12, 1:18, 1:24, 1:36, 1:72,
1:144) in CH3CN, Et4NBF4, reference electrode – Ag/AgCl.
alyst system MnIIbpy/NiIIbpy without other additional reagents.
Moreover, the yields of similar phosphorylated products were
higher (Wu – 48% under optimal conditions) [35]. Generally,
coumarins with electron-donating groups give better yields than
non-substituted coumarin does. Interestingly, 7-methylcoumarin
was the most successful substrate for phosphorylation in the 3 posi-
tion. Apparently, this is due to the +I effect of the methyl group
in combination with the +M effect of the heteroatoms. In the case
where methyl is in the 6 position, the product yield of C H substitu-
tion is lower. The reaction of non-substituted coumarin with dialkyl
H-phosphonate is also less selective than in 7-methylcoumarin. The
use of a monometallic system such as MnIIbpy and NiIIbpy will sig-
nificantly reduce the effectiveness of the target reaction and lead
to insoluble precipitates that cannot be characterized.
We have previously shown [42] that the first stage of elec-
trochemically induced phosphorylation is the formation of metal
phosphonates, which are oxidized more easily than the original
complex-catalysts. Dialkyl H-phosphonate in the test conditions is
not oxidized. Preparation electrolysis proceeds at potentials cor-
responding to the oxidation of the phosphonate complex in situ
(approximately 1.0 V).
Aromatic substrates, dialkyl H-phosphonates and Ni(BF)4bpy
complex are not paramagnetic; thus they do not give the ESR sig-
nal. The ESR spectrum of MnCl2bpy complex in solid form, like its
behavior with changes in temperature (Fig. 1), is fully consistent
with the literature data [50], which describes the polymer structure
[Mn(␮-Cl)2bpy]n. The EPR spectrum, as registered when MnCl2bpy
is dissolved in acetonitrile, is shown on the left in Fig. 2. Based on
the ratio of line breadths and the g-factor g = 2.006, |<aMn>| = 80 G,
ꢂHmI 1/2 = 10 G, it can be concluded that the spectrum belongs
=
to manganese ions [Mn2+Cl4]2− [55]. Having said that, it should
be noted that the complex is poorly soluble in acetonitrile, and
consequently a part remains in the precipitate. Nevertheless, the
intensity of the observed spectrum is small, from which it can be
concluded that, under our conditions, a significant part of the dis-
solved solution complex is not registered in the EPR X-band. This
can be explained by the presence of MnII dimers (or polymers) in
the solution, which also is confirmed by the literature data for simi-
lar complexes [56]. The addition of HP(O)(OEt)2 leads to remarkable
improvement in the solubility of MnIIbpy, while the mixture spec-
trum is a superposition of two signals, one of which is discussed
above (Fig. 2, on the right). The second signal appears to belong
to a complex with modified inner coordination manganese sphere
(the substitution of chlorides), similarly to the previously described
case [55] in the presence of H-phosphonate with the formation of
manganese phosphonate.
3.2. EPR spectroelectrochemistry
We used the ESR spectroscopy method and cyclic voltammetry
to clarify some of the details of this complex reaction.
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Subsequent to the addition of Ni(BF4)2bpy to this mix-
ture [(MnCl2bpy) + (HP(O)(OEt)2)], the ESR signal disappeared
tials with elimination of phosphonate radical, phosphorylating of
arenes, followed by regeneration of MnII и NiII.
[Mn2+Cl4]2−
. Apparently, this demonstrates the interaction
of all the components together, leading to dimers MnII-
MnII indistinguishable in the X-band ESR and the small
amount of monomeric phosphonate complex “in situ”: g = 2.006,
|<aMn>| = 96 G, ꢂHmI=1/2 = 32 G (Fig. 3). This mixture yields no
phosphonate radical (without electrochemical oxidation), since no
product of arenes phosphorylation can be formed in the absence of
electricity.
During electrolysis of the studied system in the EPR spectrom-
eter at a potential of 1.0 V, the MnII complex spectrum intensity
increases (Fig. 4).
A possible explanation of this result may be the decompos-
ing of manganese dimers at the oxidation in the presence of NiII
and (EtO)2P(O)H with the formation new monomeric intermedi-
ates MnII and its rapid regeneration in the catalytic cycle. In the
electrochemical oxidation of the reaction mixture in the EPR spec-
trum signals, which can be attributed to NiIII intermediates are not
registered. Spin-trap PBN additive in the reaction system during
electrolysis does not give a clear spectrum, and a complex interfer-
ence of spectra of several paramagnetic intermediates occurs.
4. Conclusion
We have provided a one-stage method of direct electrochem-
ical phosphorylation of aromatic C H bonds resulting in dialkyl
aryl phosphonates (aryl = benzenes, coumarins). The process takes
place under mild conditions (room temperature, normal pressure),
and at a reagent ratio of 1:1, thus providing a product with a high
yield (70%) and 100% conversion when a bimetallic catalyst system
(MnIIbpy/NiIIbpy) is used. Various benzenes bearing both electron
withdrawing and electron donating substituents on the ring were
effective substrates to afford the coupling products in good yields.
The success achieved through a fast catalytic cycle and the rapid
regeneration of metal catalysts on the electrode.
Acknowledgements
This work was supported by the grant of the Russian Science
Foundation No. 14-23-00016.
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Single-electron quasi-reversible MnCl2bpy oxidation occurs at
a potential of 1.14 V, before Ni(BF4)2bpy. By adding a diethyl H-
phosphonate to MnCl2bpy complex solution (Fig. 5a), we observed
a peak shift to less anode potential (0.9 V), but the current in this
peak increases with increasing HP(O)(OEt)2 content in the solu-
tion reaching icat/ip = 21 at a ratio of 1:168. This demonstrates the
rapid regeneration of MnIIbpy in the catalytic oxidation reaction of
the phosphonate. Ni(BF4)2bpy voltammograms in the presence of
increasing amounts of HP(O)(OEt)2 are similar (Fig. 5b), although
the current gains are less. The potential of Ni(BF4)2bpy shifted on
70 mV to the cathodic area, and after a 36-fold excess of acid the
current ceases to increase. The maximum ratio of icat/ip is 1.6. Thus,
the observed changes in the redox properties of original metal
complexes in the presence of dialkyl H-phosphonate are probably
associated with strong coordinating properties of it [57,58] as well
as the formation of phosphonates metals, which oxidize more eas-
ily than the original complex would. Dialkyl H-phosphonate and
benzene in the test conditions show no oxidation waves. Benzene
additives have no effect on the potentials and currents of the cat-
alytic waves on voltammograms.
To compare the catalytic efficiency of systems containing nickel
and manganese (or the mixture thereof), we chose the same con-
ditions (Table 3), i.e., the ratio of [Mbpy]: [HP(O)(OEt)2] 1:6. The
greatest catalytic current increase in icat/ip (Table 3) was observed
in the case of a metal catalyst mixture (Fig. 4) in comparison with
the individual complexes MX2bpy, which was confirmed by prepar-
ative electrolysis data where a high yield was obtained only with
the participation of two metals and their synergetic action.
We can assume that the catalytic cycle involves the following
scheme (Scheme 2):
The mechanism of the process requires further research,
although the initial stage of the cycle can assumed the formation of
the metal (or metals) phosphonate, oxidized at low anodic poten-
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Please cite this article in press as: M.N. Khrizanforov, et al., Novel approach to metal-induced oxidative phosphorylation of aromatic
compounds, Catal. Today (2016), http://dx.doi.org/10.1016/j.cattod.2016.06.001