Synthesis of Dimethyl Phenylphosphonates Catalyzed by Group VI Metal(0) Hexacarbonyls

Article abstract of DOI:10.1134/S1070428018110234

The coupling of dimethyl phosphite and iodobenzene occurs in the presence of catalytic amounts of homoligand carbonyl complexes of chromium subgroup metals to form dimethyl phenylphosphonate in yields of 50–73% depending on the metal.

Full text of DOI:10.1134/S1070428018110234

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2018, Vol. 54, No. 11, pp. 1746–1748. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © A.I. Kuramshin, A.V. Plotnikova, M.V. Adel’shina, V.I. Galkin, 2018, published in Zhurnal Organicheskoi Khimii, 2018, Vol. 54,
No. 11, pp. 1727–1728.
SHORT
COMMUNICATIONS
Synthesis of Dimethyl Phenylphosphonates Catalyzed
by Group VI Metal(0) Hexacarbonyls
A. I. Kuramshina, A. V. Plotnikovaa, M. V. Adel’shinaa, and V. I. Galkina*
a Kazan (Volga Region) Federal University, ul. Kremlevskaya 18, Kazan, 420008 Tatarstan, Russia
*e-mail: fea_naro@mail.ru
Received March 14, 2018
Revised March 14, 2018
Accepted March 14, 2018
Abstract—The coupling of dimethyl phosphite and iodobenzene occurs in the presence of catalytic amounts of
homoligand carbonyl complexes of chromium subgroup metals to form dimethyl phenylphosphonate in yields
of 50–73% depending on the metal.
DOI: 10.1134/S1070428018110234
Organophosphorus compounds attract attention due
to their broad-range potential practical [1]. Arylphos-
phonates can serve as intermediates in the synthesis of
functionalized organophosphorus compounds [2] and
can be used as pharmacologically active compounds
[3]. The use of arylphosphonates in the design of new
materials has been reported [4]. They have also been
used as organoelement catalysts [5]. A lot of catalytic
syntheses of organophosphorus compounds, including
those from hydrocarbons, are known [6].
According to the 31Р NMR data, a complete
conversion of dimethyl phosphite took place. The 31Р
NMR spectrum of the reaction mixture displayed a
single signal at δ 22.7 ppm, which, according to
published data [13], was signed to phosphorus in
dimethyl phenylphosphonate. Apparently, dimethyl
phenylphosphonate that forms leaves the coordination
sphere of chromium, while chromium(0) hexacarbonyl
or its transformation product catalyzes formation of
dimethyl phenylphosphonate.
P-Arylation allows synthesis of aromatic organophos-
phorus compounds, first of all arylphosphines, which are
the most common ligands in transition metal complex
catalysts [7]. There is a present tendency to replace Pt
and Pd catalysts of Р–С bond-forming reactions [8] by
derivatives of less costly metals, specifically copper [9,
10]. The stoichiometric dechlorophosphorylation of
chlorobenzene incorporated in the (η6-C6H5Cl)Cr(CO)3
complex [11]; the resulting diethyl phenylphosphonate
does not leave the coordination sphere of chromium.
To find evidence for this suggestion, we synthe-
sized dimethyl phenylphosphonate by reacting
iodobenzene with dimethyl phosphite in the presence
of catalytic amounts of chromium hexacarbonyl and
other homocarbonyl Group VI metal complexes
(Mo, W).
With all the three metal hexacarbonyls, the 31P
NMR spectra of the reaction mixtures showed signals
of the main reaction product, an organophosphorus
compound which gives a singlet at δ 22.7 ppm. In the
case of Cr(CO)6, the reaction product, dimethyl
phosphonate 1, could be isolated (see scheme).
In view of the fact that arenetricarbonyl complexes
of chromium subgroup metals can form be formed
upon refluxing solutions of metal(0) hexacarbonyls in
high-boiling arenes [12], we reacted dimethyl phosphite
with the (η6-C6H5I)Cr(CO)3 complex formed in situ from
chromium(0) hexacarbonyl in iodobenzene under reflux,
in the presence of trimethylamine (the organometallic
compound, dimethyl phosphite, and trimethylamine
were taken in a 1 : 1.2 : 1.2 molar ratio).
O
I
P(OCH3)2
NEt3_M(CO)6
+ (CH3O)2P(O)H
1
M = Cr, Mo, W.
1746

SYNTHESIS OF DIMETHYL PHENYLPHOSPHONATES CATALYZED BY GROUP VI
1747
1
Conversions of dimethyl phosphite and yields of dimethyl
phenylphosphonate in Group VI metal complex-catalyzed
reactions (31Р NMR data)
The Н NMR spectrum of compound 1 displays
doublets at δ 3.78 ppm, 3J(P,OCH3) 11.0 Hz, assignable
to methoxyl protons, and a multiplet at 7.40–7.80 ppm,
assignable to phenyl protons. In the 13С NMR spectra,
the signals of these groups are observed at δ 53 and
127–139 ppm, respectively. The boiling point and
refractive index of the isolated compound, as well as
its 31P NMR chemical shift are consistent with those
reported in [13] for dimethyl phenylphosphonate. The
elemental analysis of compound 1, too, is consistent
with the proposed structure.
Conversion of
Yield of dimethyl
Catalyst
dimethyl phosphite, phenylphosphonate 1,
%
%
Cr(CO)6
Mo(CO)6
W(CO)6
100
96
74
57
56
50
NMR spectrum (C6D6), δ, ppm: 11.0 d [(CH3)P(O)H,
1JPH 693 Hz], 22.7 s [(CH3)P(O)Ph].
According to the 31Р NMR data, Group VI metal
carbonyl complexes differ in the efficiency to catalyze
the iodoarene deiodophosphorylation reaction. Under
the same reaction conditions, the replacement of
Cr(CO)6 by W(CO)6 decreases the conversion of
dimethyl phosphite and the yield of dimethyl
phenylphosphonate (see table).
b. Iodobenze, 11.25 mL (0.1 mol), dimethyl
phosphite, 9.0 mL (0.1 mol), trimethylamine, 14.0 mL
(0.1 mol), and 2.2 g (0.01 mol) of chromium(0)
hexacarbonyl were placed into a 50-mL flask. The
resulting mixture was refluxed for 5 h, and then
worked up to isolate dimethyl phenylphosphonate,
yield 13.6 g (73%). The physical and physicochemical
characteristics of the product were identical to those in
[13].
We explain the decrease of the catalytic activity of
the М(СО)6 complexes with increasing charge of the
metal by the decreasing rate of formation of
arenetricarbonyl complexes in the reaction of arene
with metal hexacarbonyl in the series chro-
mium>molybdenum>tungsten [14]. Presumably, the
activity of the discovered catalytic system is controlled
by the rate of formation of the (η6-C6H5I)M(CO)3
complexes in the PhI–M(CO)6 system. As known, the
(η6-ArX)M(CO)3 complexes undergo a rather facile
nucleophilic substitution of halogen by the SNAr
mechanism [8, 15].
1
The H NMR spectra were measured on a Bruker
Avance III 400 instrument (400.0 МHz) in
deuterobenzene-d6; the chemical shifts were measured
against residual proton signals of the deuterated
solvent. The 31Р NMR spectra were run on a Bruker
Avance III 400 spectrometer (161.9 МHz), external
reference 85% aqueous Н3РО4. The 13C NMR spectra
were obtained on
a
Bruker Avance III 400
spectrometer (100.4 МHz), internal reference
deuterobenzene-d6.
Further, we are going to study the mechanism of the
discovered catalytic reaction in more detail and expand
its synthetic potential by involving in this catalytic
coupling other hydrophosphoryl compounds and
iodoarenes.
FUNDING
The work was funded from the State subsidy
allocated to the Kazan (Volga region) Federal
University for enhancing its competitiveness among
the world leading research and educational centers.
Commercial dimethyl phoshite and iodobenzene
were purified by standard procedures. Commercial
metal(0) hexacarbonyls were purified by vacuum
sublimation (5×10–2 mmHg) at 60–80°С.
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