Phosphorylation of trihydroxybenzenes with the trivalent phosphorus derivatives

Article abstract of DOI:10.1134/S107036321106003X

Phosphorylation of the simplest trihydroxybenzenes and their acylated derivatives with the trivalent phosphorus reagents of cyclic and acyclic structure was discussed. A possibility of the selective phosphorylation of acylated trihydroxybenzene derivatives was demonstrated. A dismutation was detected, leading to dimers of the linear structure containing a variety of phosphorus-containing fragments of different nature. Pleiades Publishing, Ltd., 2011.

Full text of DOI:10.1134/S107036321106003X

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 6, pp. 1081–1091. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © E.N. Rasadkina, S.A. Toloraya, P.V. Slitikov, E.E. Nifant’ev, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 6,
pp. 887–897.
Phosphorylation of Trihydroxybenzenes
with the Trivalent Phosphorus Derivatives
E. N. Rasadkinaa, S. A. Tolorayaa, P. V. Slitikovb, and E. E. Nifant’eva
a Moscow State Pedagogical University, Chemistry Department, Nesvizhskii per. 3, Moscow, 119021 Russia
fax: (495)2467766
e-mail: chemdept@mail.ru
b Bauman Moscow State Technical University, Moscow, Russia
e-mail: pavlasiy@mail.ru
Received May 13, 2010
Abstract—Phosphorylation of the simplest trihydroxybenzenes and their acylated derivatives with the tri-
valent phosphorus reagents of cyclic and acyclic structure was discussed. A possibility of the selective phos-
phorylation of acylated trihydroxybenzene derivatives was demonstrated. A dismutation was detected, leading
to dimers of the linear structure containing a variety of phosphorus-containing fragments of different nature.
DOI: 10.1134/S107036321106003X
Polyatomic phenols are widely used in fine organic
synthesis. On their basis macrocyclic systems are
created such as cryptands, spherands and calixarenes
used in various branches of science, medicine and
technology [1, 2]. It is essential that the introduction
into such systems of the phosphorus atom can signi-
ficantly extend the range of their functional applica-
tion. On the basis of the phosphorus-containing polyols
unusual supramolecular systems [3] and polydentate
ligands were synthesized used for the creation of
transition metal complexes [4, 5].
Continuing our research on the phosphorylation of
phenols [6–8], we planned the synthesis of a series of
acyclic ligands containing in their composition
alongside the aromatic rings three or more phosphorus-
containing fragments of different structure and degree
of oxidation of the phosphorus atom. As the initial
compounds for the design of the ligands of this type
we selected the geometrically simplest rigid system of
trihydroxybenzenes, with the hydroxy groups located
in different positions.
OH
OH
HO
OH
OH
HO
OH
OH
OH
Pyrogallol
Oxyhydroquinone
Phloroglucinol
1,2,3-trihydroxybenzene
1,2,4-trihydroxybenzene
1,3,5-trihydroxybenzene
The first stage of the synthesis of the above multi-
functional ligands consisted in the study of phos-
phorylation of the initial aromatic triols since these
processes were not practically described. It is known
that phosphorylation of oligohydroxy compounds, both
of the aromatic [9–11] and aliphatic [12–14] type,
leads mostly either to perphosphorylated products, or
to the formation of phosphocyclic systems (in the
presence of closely spaced hydroxy groups). If the
ratio of reagents does not match the number of
hydroxy groups in the original molecule, a mixture of
products is formed [15].
The present research was initiated to study the
phosphorylation of trihydroxybenzenes with the ortho-
located hydroxy groups, pyrogallol (I) and
oxyhydroquinone (II), which are similar chemically to
pyrocatechol. From the literature it is known that
1081

1082
RASADKINA et al.
phosphorylation of the last compound even with an
excess of phosphorous di- or triamide leads to the
formation of 1,3,2-dioxybenzophospholane [16, 17],
and the phosphorylation with the cyclochlorophos-
phites of phosphorinane type, to the formation of
relatively stable dicyclophosphites. However, their
distillation in a high vacuum, or storage in air leads to
decomposition [18]. On the other hand, it was shown
that phosphorylation of pyrocatechol and pyrogallol
mole of phosphorous triamide. We expected to get a
cyclic system containing mutually unbound hydroxy
and amide fragments. Then it was anticipated to use
the third hydroxy group for the prophosphorylation
with another phosphorylating reagent. As the initial
phosphorylating reagents we used phosphorous
hexamethyl- (IIIa) and hexaethyltriamides (IIIb). As a
result of this reaction formed 1,3,2-dioxaphospholanes
(IVa, IVb) that produce in 31P NMR spectrum a
singlet signal at 151 ppm characteristic of the amido-
phospholane ring. However, they are extremely un-
stable at keeping in solution, and the attempted
isolation leads to decomposition of the phosphorus-
containing fragment. We suggest that this is due to the
intermolecular interaction of free hydroxy groups to
form a ring.
with
2-diethylamido-5,5-dimethyl-1,3,2-dioxaphos-
phorinane at room temperature at the equimolar ratio
of reagents led to the formation of hexacoordinated
phosphorus derivatives [19].
We regarded as interesting to carry out phos-
phorylation of trihydroxybenzenes I and II with one
O
O
OH
P
Oxidation and destruction
NR2
+
P(NR2)3
OH
HO
HO
I, II
IIIa, IIIb
IVa, IVb
R = Me (a), Et (b).
In order to prevent such reactions, we decided to
protect the hydroxy groups remaining in the parent
molecule, but in a way not preventing phosphorylation.
For such protection the acyl derivatives are suitable,
which can be phosphorylated with phosphorous amides
but at a lower rate [20].
hexaethyltriamide at a ratio of reagents 1:1. Note that
phosphorylation with phosphorous hexaethyltriamide
in different solvents and at different temperatures did
not lead to positive results.
The reaction with phosphorous hexamethyltriamide
in dioxane completed in 2 days at room temperature.
The 31P NMR spectrum of the reaction solution showed
the signal at 150 ppm typical of the phospholane ring
with amide substituents at the phosphorus atom.
The phosphorylation of pyrogallol triacetate (V)
and oxyhydroquinone triacetate (VI) was carried out
with phosphorous hexamethyltriamide or phosphorous
OAc
O
O
O
NMe2
S
P(NMe2)3
S
Ac2O
NMe2
P
P
I
OAc
O
OAc
VII
OAc
AcO
VIII
V
S
P
O
NMe2
NMe2
OAc
P
O
O
O
O
O
OAc
P(NMe2)3
S
Ac2O
OAc
VI
OAc
OAc
IX
X
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PHOSPHORYLATION OF TRIHYDROXYBENZENES
1083
The structure of the compounds obtained was
confirmed after the the sulfurization of the reaction
mixture and chromatographic separation of thiono-
phosphates VIII and X. In the 31P NMR spectra two
The obtained compounds VIII and X are stable and
can be used in future for the introduction of other
phosphorus substituents and produce structures with
mixed phosphorus functions.
1
singlet signals were observed at 87–89 ppm. In the H
At the phosphorylation of trihydroxybenzenes I and
II with two moles of phosphorous triamide (IIIa or
IIIb) in acetonitrile or dioxane the reaction ends in
NMR spectrum of compound X there are singlet signals
of methyl protons of acyl groups (δ 2.88 ppm), a doublet
signal of methyl protons of amide group (δ 2.87 ppm)
as well as two doublets and a singlet of the protons of
aromatic fragment (δ 6.71, 6.86, 7.03 ppm, respec-
tively), while for the protons H3 and H5 the meta-
coupling constants 4JHH 2.4 Hz were observed. Integral
curve corresponded to this distribution of protons.
31
2 days at room temperature. In the P NMR spectrum
of the reaction solution three signals appeared
simultaneously: at 151 and 144 ppm, typical of mono-
amidoester, and at 137 ppm, characteristic of phos-
phorous diamidoester.
OH
O
O
NR2
S
S
P NR2
+ 2 P(NR2)3
OH
P
O
O
HO
(R2N)2PO
(R2N)2PO
S
XIb, XIIа, XIIb
I, II
IIIа, IIIb
XIIIb, XIVа, XIVb
For a more reliable identification of the compounds
obtained they were brought into the sulfurization. The
reaction was carried out at room temperature over
2 days. The products XIIIb, XIVa, and XIVb were
isolated by column chromatography as oily substances.
Yields were quite small, not exceeding 22%. In their
31P NMR spectra two singlet signals were observed at
89–90 and 74–79 ppm, with a ratio of integral
Upon storage the reaction solution of compounds
XIb and XIIa, XIIb, the signal at 144 ppm in the 31P
NMR spectra increased. After keeping them for 3 days
(methyl derivative XIIa) or 10 days (ethyl derivatives
XIb, XIIb) at room temperature we performed the
sulfurization of the reaction mixture. The thio
derivatives XVIIb, XVIIIa, and XVIIb were isolated
by column chromatography and identified as dimer
compounds with two benzamidophospholane rings in
their composition (δP 89–90 ppm) and one acyclic
monoamide fragment (δP 74–79 ppm), integral
intensities ratio was 2: 1.
1
intensities 1:1. In the H NMR spectrum the signals of
all groups of protons were registered with an estimated
ratio of the integral intensities, but all the protons were
nonequivalent.
O
O
O
P NR2
XIb, XIIa, XIIb
R2N P
_P(NR2)3
O
O
O
P
NR2
XVb, XVIa, XVIb
O
S
O
O
R2N
S
P
P
NR2
S
O
S
P
O
O
NR2
XVIIb, XVIIIa, XVIIIb
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 6 2011

1084
RASADKINA et al.
1
In the H NMR spectrum of compounds XVIIb,
XVIIIa, and XVIIIb there were the signals of all groups
of protons. Integration of the signals showed that four
alkyl groups belong to the cyclic molecular fragments,
and two to acyclic. In addition, in the MALDI–TOF
mass spectrum of compound XVIIb there was a peak
at m/z 651 corresponding to the calculated one, which
also indicated that these systems are dimeric.
hoping to use the resulting product for further
synthesis of “double-decked” system. The reaction was
carried out in acetonitrile at room temperature.
After 45 min the reaction completed, and in the 31P
NMR spectrum one singlet signal was observed with
δP 132.2 ppm (XVIII), typical of diamidophosphites.
After the sulfurization of the reaction mass and
chromatographic purification product XIX was isolated,
which was an oily substance containing in its 31P NMR
spectrum one singlet signal at 74.2 ppm, typical of
Thus, it was shown that in this case the dismutation
[21] of two molecules of compounds XIb, XIIa, and
XIIb proceeds with the formation of dimeric products
containing three phosphoric centers of different
structures. This provides a possibility to use the
compounds of this type in the future as three-centered
ligands for the synthesis of metal complexes.
1
thionodiamidophosphates. In its H NMR spectrum a
triplet of methyl groups in the region of 1.13 ppm, a
multiplet of methylene protons at 3.20 ppm, and a
singlet of aromatic protons in the region of 6.51 ppm
were detected. Some nonequivalence of methylene
protons of ethyl groups should be noted, leading to the
presence of two doublet signals elucidated by the
method of double magnetic resonance (3JPH 12.6 and
11.6 ppm).
1,3,5-Trihydroxybenzene, or phloroglucinol (XVII),
is an interesting object for the creation of not only
three-centered ligands, but of the phosphomacrocyclic
systems, because it has three distant in space hydroxy
groups. Data on its phosphorylation were not found in
the literature.
At the storage of acetonitrile solution of compound
XVIII over 45 min, in its 31P NMR spectrum a signal
appeared at 140.4 ppm indicating the dismutation of
the formed perphosphorylated XVIII.
The study was started with the perphosphorylation
of phloroglucinol with phosphorous hexaethyltriamide,
S
OH
OP(NEt2)2
OP(NEt2)2
P(NEt2)3
S
HO
OH
OP(NEt2)2
(Et2N)2PO
(Et2N)2PO
S
OP(NEt2)2
S
XVIII
XIX
XVII
_3P(NEt2)3
H3C
CH2
CH3
CH2
O
O
P
P
N
CH3
CH3
N
CH2
CH2
O
O
CH2
O
H3C
P
N
O
CH2
H3C
XX
Upon the reaction completion, an oily substance
precipitated insoluble in common organic solvents, but
swelling in DMF indicating the formation of a cyclic
dimeric product XX, or a cross-linked oligomer. The
phosphorylation of phloroglucinol with one or two
moles of phosphorous triamide resulted in similar
oligomeric products.
The preparation of the mono- and diphosphorylated
systems based on phloroglucinol was performed on
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 6 2011

PHOSPHORYLATION OF TRIHYDROXYBENZENES
1085
1,3,5-triacetoxybenzene (XXI) obtained by the usual
method. The phosphorylation with the phosphorous
triamides was carried out at the ratio of reagents 1:1
and 1:2.
140.3 ppm is observed, indicating either a very rapid
dismutation of the formed compounds XXIIa and
XXIVa, or the interaction of these diamides with acyl
groups of adjacent molecules, but we have not yet
studied this reaction. In the course of the reaction the
formation of precipitates occurred insoluble in organic
solvents, which makes them inappropriate for
identification.
At the mono- and diphosphorylation of compound
XXI with phosphorous hexamethyltriamide the
appearance in the 31P NMR spectrum of a signal at
S
OP(NR2)2
OP(NR2)2
S
1:1
OAc
AcO
OAc
AcO
AcO
OAc
XXIIа, XXIIb
XXIIIb
Ac2O
XVII
+ P(NR2)3
S
OP(NR2)2
AcO
OP(NR2)2
OAc
S
XXI
1:2
AcO
XXIVа, XXIVb
R = CH3 (a), C2H5 (b).
OP(NR2)2
OP(NR2)2
S
XXVb
At the use of phosphorous hexaethyltriamide mono-
(XXIIIb) and diphosphorylated (XXVb) products
were isolated by column chromatography after the
sulfurization. In the 31P NMR spectrum of compound
XXIIIb a singlet signal appeared at δP 74.1 ppm. In the
1H NMR spectrum a triplet signal was observed of
methyl protons of ethyl group (1.15 ppm) and a singlet
signal of methyl protons of acyl groups (2.30 ppm), a
multiplet of methylene protons of ethyl group
(3.22 ppm), and two singlets of the protons of aromatic
rings (6.72 ppm and 6.87 ppm). Integral intensities of
the signals of methyl protons corresponded to six
protons of acyl groups and twelve protons of amide
groups. Apart from that, the 13C NMR spectra were
obtained and the molecular weight was measured by
MALDI-TOF mass spectrometry, which confirmed the
formation of the monophosphorylated product.
To avoid dismutation which leads to the formation
of oligomeric systems, we carried out phosphorylation
of trihydroxybenzenes I, II, and XVII with ethyl
tetraethyldiamidoethylphosphite EtOP(NEt2)2. This
reaction should lead to the formation of monoamides
that at room temperature do not enter in further
transformations. However, we succeeded to perform
this reaction only with phloroglucinol XVII. The
phosphorylation of pyrogallol I and oxyhydroquinone
II resulted in the formation of bright-colored insoluble
precipitates, inappropriate for identification.
The phosphorylation of phloroglucinol XVII was
carried out in dioxane at a ratio of reagents 1: 2 over
1 day. From the reaction a mixture of products was
obtained consisting of di- and triphosphorylated
phloroglucinol XXVI and XXVII, while according to
the 31P NMR spectrum of the reaction mixture, the
mixture contained 85% only of the desired product
XXVI.
Similar methods were used for the identification of
compound XXVb. It was proved that this compound
was diphosphorylated and contained two phosphamide
fragment and one acyl group.
After the the sulfurization, the thionphosphates
XXVIII and XXIX were isolated by column chro-
matography. These compounds are oily substances. In
their 31P NMR spectra a signal at 72 ppm was observed
characteristic of thionophosphoric monoamidoesters.
Thus, the presence in compounds XXIIb–XXVb of
acyl groups makes it possible to introduce into the
molecule the other phosphoric centers.
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1086
RASADKINA et al.
OРNEt2(OEt)
OРNEt2(OEt)
+
XVII + 2 EtOP(NEt2)2
OH
(EtO)Et2NРO
(EtO)Et2NРO
OРNEt2(OEt)
XXVI
XXVII
S
S
OРNEt2(OEt)
OРNEt2(OEt)
S
+
OH
XXVIII
(EtO)Et2NРO
OРNEt2(OEt)
(EtO)Et2NРO
S
S
S
XXIX
1
They were also were characterized by H and 13C
carried out in dioxane at 50°C, at the reagent ratio 1: 2
for 15 days. In the 31P NMR spectrum of the reaction solu-
tion the slow accumulation was observed of the signal
of cyclic phosphorous triester (δP 115.4 ppm). The
sulfurization of the compounds formed was carried out
for 7 days at room temperature. After the reaction com-
pletion, in the 31P NMR spectrum of the reaction mix-
ture a singlet signal at 53 ppm was detected, but the chro-
matography indicated the presence of two products.
NMR spectroscopy.
For the same purpose, at the the phosphorylation of
phloroglucinol XVII we used alkylenephosphorous
amides and chlorides like neopentylene tetraethyl-
amidophosphite (XXX), propylene and neopentylene
chlorophosphites (XXXIII) and (XXXIV).
The reaction with amidophosphite XXX was
CH3
CH3
O
O
S
CH3
CH3
O
O
S
P
P
O
O
CH3
CH3
O
S
XVII + 2Et2N
+
P
O
O
P
O
O
XXX
HO
O
P
S
S
O
P
O
S
O
O
O
CH3
CH3
H3C
H3C
CH3
H3C
XXXI
XXXII
Compounds XXXI and XXXII were isolated
chromatographically and characterized by NMR
spectroscopy as di- (XXXI) and triphosphorylated
(XXXII) oily and powdery substances, respectively.
(XXXIV) at the ratio of reactants 1:1 in the presence
of triethylamine as an acceptor of hydrogen chloride
only a trisphosphorylated product formed, but a part of
the original trihydroxybenzene (XVII) remained in
solution unused. Moreover, such a direction of the
reaction does not depend on the order of mixing the
reagents. This is due, we think, to the high rate of the
the phosphorylation with the chlorophosphites.
1
To the desired compound XXXI in H NMR spectrum
corresponded the signals of axial and equatorial protons
of methyl groups at 1.08 and 1.32 ppm, respectively,
and the signals of axial and equatorial protons of
methylene groups in the region of 4.04, 4.32 ppm with
the respective spin–spin coupling constants 2JHH and 3JPH.
At introducing two moles of a chlorophosphite
XXXIII or XXXIV bisphosphorylated product XXXV
or XXXVI formed, respectively. The products were
isolated after the sulfurization and were characterized
With the phosphorylating reagent propylene
(XXXIII)
and
neopentylene
chlorophosphites
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 6 2011

PHOSPHORYLATION OF TRIHYDROXYBENZENES
1087
1
by 31P, H, and 13C NMR spectroscopy. Bisthiono-
by the reaction with amide, but the yield of the
desired product in the case of the chloride method was
higher.
phosphate XXXI according to its physicochemical
characteristics was identical to that obtained previously
S
O
O
R
P
R
P
O
O
O
O
O
NEt3
S
XVII + 2 R
P
Cl
NEt3 HCl
O
HO
O
HO
O
O
O
R
R
P
P
O
O
S
XXXIII, XXXIV
XXXV, XXXVI
XXXI, XXXVII
CH3
CH3
R =
(XXXIII, XXXV, XXXVII);
(XXXI, XXXIV, XXXV).
Thionophosphate XXXVII was also obtained as an
oily substance. In its 31P NMR spectrum a singlet was
observed at 55.7 ppm, characteristic of cyclic thiono-
of the aromatic protons, with the ratio of integral inten-
sities 1:2, and the signal of the proton of hydroxy group.
1
The isolated thionophosphates XXXI and XXXVII
can be entered in the phosphorylation with equimolar
amount of phosphorous hexaethyltriamide at room
temperature, as was illustrated by an example of
thionophosphate XXXI.
phosphates. In the H NMR spectrum multiplets were
observed of equatorial and axial methylene protons in
the fifth position of the ring, at 1.85 and 2.23 ppm,
respectively, of the equatorial and axial methylene protons
in 4 and 6 positions of the ring in the region of 4.51 ppm,
CH3
O
O
CH3
CH3
O
O
S
S
P
P
O
O
CH3
NEt2
C
C
H3C
O
O
S
S
S
P
2XXXI + P(NEt2)3
P
P
O
O
O
O
O
O
H3C
S
After stirring for 15 days in dioxane sulfur was
added to the solution and the resulting product
XXXVIII was isolated. In its 31P NMR spectrum two
singlet signal were observed with δP 53.2 and
65.3 ppm, with the ratio of integral intensities 4:1. The
formation of dimeric product XXXVIII was confirmed
by the 1H NMR spectrum.
case cannot be involved into the reaction. On the other
hand, using acyl derivatives of trihydroxybenzenes, in
particular, of phloroglucinol, free acyl group can be
further replaced by other phosphorous sites.
EXPERIMENTAL
1
The H, 13C (CDCl3) and 31P NMR spectra were
obtained on a JEOL ECX-400 instrument (400 MHz),
Thus, we can conclude that the most successful in
the synthesis of initial compounds for the molecular
assembling is the phosphorylation of 1,2,3- and 1,2,4-
trihydroxybenzenes with phosphorous amides at a ratio
of reagents 1:2. However, another amide center in this
1
the H and 13C chemical shifts are given relative to
TMS, the 31P shifts, relative to 85% phosphoric acid.
Mass-spectral studies were performed on a Bruker
Ultra Flex instrument with a time-on-flight (TOF)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 6 2011

1088
RASADKINA et al.
detector by the method of matrix-activated laser
desorption and ionization (MALDI) (λ 337 nm) using
trihydroxyanthracene as a matrix.
H 4.39; N 5.07; P 11.36. C10H12NO4PS. Calculated, %:
C 43.96; H 4.43; N 5.13; P 11.34.
2-Thiono-2-(dialkylamino)benzo[d][1,3,2]dioxa-
phosphol)-4- or 5-yl N,N,N',N'-tetraalkyldiamino-
thionophosphates (XIIIb, XIVa, XIVb) To 1.6 mmol
of 1,2,3- or 1,2,4-trihydroxybenzene (I, II) dissolved
in 5 ml of acetonitrile or dioxane, was added 3.2 mmol
of phosphorous hexamethyltriamide or phosphorous
hexaethyltriamide at room temperature at continuous
stirring. After two days to the reaction mixture 3.2 mmol
of sulfur was added and the mixture was stirred for
another two days. Then the solvent was evaporated and
the residue was chromatographed on a column, the
products XIIIb, XIVa, XIVb were eluted with ben-
zene. The obtained products were dried in a vacuum
(1 mm Hg, 70ºC).
All syntheses involving compounds of trivalent
phosphorus were carried out in an atmosphere of dry
argon. The adsorption column chromatography was
carried out on silica gel L 100–250 mm; Rf values were
determined by TLC on the Silufol UV-254 plates using
the systems: hexane–dioxane 3:1 (A), hexane–dioxane
5:1 (B), benzene–dioxane 3:1 (C). The substances
were detected by iodine vapor and calcination.
Phosphorous hexamethyl- (IIIa) and hexaethyl-
triamides (IIIb) were obtained by the method [22].
Pyrogallol (V) and phloroglucinol (XVII) triacetates
were obtained by the method [23], oxyhydroquinone
triacetate (VI) by [24]. Ethyl phosphorous tetraethyl-
diamide was obtained by the method [25], 5,5-di-
methyl-2-diethylamide-1,3,2-dioxaphosphorinane (XXX),
by the method [26], 2-chloro-1,3,2-dioxaphos-
phorinane (XXXIII) and 2-chloro-5,5-dimethyl-1,3,2-
dioxaphosphorinane (XXXIV), by the method [27].
2-Thiono-2-(diethylamino)benzo[d][1,3,2]dioxa-
phosphol)-4-yl N,N,N',N'-tetraethyldiaminothiono-
phosphate (XIIIb), yield 42%, oily substance, Rf 0.65
1
(C). H NMR spectrum, δ, ppm: 1.15 m (12H, CH3,
3
3JHH 7.3 Hz), 1.18 m (6H, CH3, JHH 5.8 Hz), 3.17 m
(8H, CH2, 3JPH 12.4 Hz), 3.30 m (4H, CH2, 3JPH 13.2 Hz),
6.84–6.90 m (3H, CH). 31P NMR spectrum, δP, ppm:
88.0, 78.7 (C6H6). Found, %: C 46.44, H 7.14; N 9.03;
P 13.31. C18H33N3O3P2S2. Calculated, %: C 46.48; H
7.13; N 9.00; P 13.34.
2-Thiono-2-(dimethylamino)benzo[d][1,3,2]di-
oxaphosphol)-4- or -5-yl acetates (VIII, X). To 0.79
mmol of 1,2,3- or 1,2,4-triacetoxybenzene (V, VI)
dissolved in 5 ml of dioxane was added 0.79 mmol of
phosphorous hexamethyltriamide while continuous
stirring at room temperature. After 2 days 0.79 mmol
of sulfur was added to the solution. After another day
the solvent was evaporated, and the residue was
chromatographed on a column, eluting compounds
VIII, X with hexane. The isolated products were dried
in a vacuum (1 mm Hg, 70ºC).
2-Thiono-2-(dimethylamino)benzo[d][1,3,2]di-
oxaphosphol)-5-yl N,N,N',N'-tetramethyldiamino-
thionophosphate (XIVa), yield 22%, oily substance,
Rf 0.40 (A). 1H NMR spectrum, δ, ppm: 2.72 d.d (12H,
CH3, 3JPH 11.9, 12.2 Hz, 4JHH 1.5, 1.2 Hz), 2.76 d (6H,
3
3
CH3, JPH 12.5 Hz ), 6.70 d.d (1H, CH, JHH 8.6 Hz,
4JHH 1.6 Hz), 6.85 d (1H, CH, 4JHH 1.5 Hz), 6.98 d (1H,
2-Thiono-2-(dimethylamino)benzo[d][1,3,2]di-
oxaphosphol)-4-yl acetate (VIII), yield 80%, mp. 63–
CH, JHH 8.6 Hz). 31P NMR spectrum, δP, ppm: 89.8,
3
81.9 (C6H6). Found, %: C 37.79; H 5.55; N 11.02; P,
16.24. C13H21N3O3P2S2. Calculated, %: C 37.71; H
5.53; N 11.07; P 16.30.
1
64ºC, Rf 0.54 (A). H NMR spectrum, δ, ppm: 2.32 s
3
(3H, CH3), 2.81 d (6H, CH3–N, JPH 12.4 Hz), 6.63 d
(1H, CH, 3JHH 8.4 Hz ), 6.78 dd (1H, CH, 3JH3H1 7.3 Hz,
4JHH 2.6 Hz), 6.94 m (1H, CH, 3JHH 8.4 Hz). P NMR
spectrum, δP, ppm: 90.0 (CHCl3). Found, %: C 43.82,
H 4.42; N 5.13; P 11.35. C10H12NO4PS. Calculated, %:
C 43.96; H 4.43; N 5.13; P 11.34.
2-Thiono-2-(diethylamino)benzo[d][1,3,2]dioxa-
phosphol)-5-yl N,N,N',N'- tetraethyldiaminothiono-
phosphate (XIVb), yield 21%, oily substance, Rf 0.58
1
(A). H NMR spectrum, δ, ppm: 1.11 m (12H, CH3),
1.14 m (6H, CH3, 3JHH 7.8 Hz), 3.18 m (8H, CH2), 3.40
m (4H, CH2, 3JPH 11.7 Hz), 6.87–6.93 m (3H, CH). 31P
NMR spectrum, δP, ppm: 88.0, 78.6 (C6H6). Found, %:
C 46.44, H 7.14; N 9.03; P 13.31. C18H33N3O3P2S2.
Calculated, %: C 46.48; H 7.13; N 9.00; P 13.34.
2-Thiono-2-(dimethylamino)benzo[d][1,3,2]di-
oxaphosphol)-5-yl acetate (X), yield 71%, oily sub-
1
stance, Rf 0.27 (B). H NMR spectrum, δ, ppm: 2.28 s
3
(3H, CH3), 2.87 d (6H, CH3, JPH 12.5 Hz), 6.71 d.d
3
4
(1H, CH, JHH 8.5 Hz, JHH 2.4 Hz), 6.86 d (1H, CH,
4JHH 2.4 Hz), 7.03 d (1H, CH, JHH 8.6 Hz). 31P NMR
spectrum, δP, MD: 87.5 (CHCl3). Found, %: C 43.91,
Bis(2-thiono-2-(dialkylamino)benzo[d][1,3,2]di-
oxaphosphol-4- or 5-yl) dialkylaminothionophos-
3
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PHOSPHORYLATION OF TRIHYDROXYBENZENES
1089
phates (XVIIb, XVIIIa, XVIIIb). After keeping the
reactive solution of the compound XIIa for 3 days, or
compounds XIb, XIIb for 10 days at room
temperature, to the reaction mixture was added 5 mmol
of sulfur and the mixture was kept at room temperature
for 3 days. The compounds formed were isolated by
column chromatography, eluting the products XVIIb,
XVIIIa, and XVIIIb with benzene. The obtained
products were dried in a vacuum (1 mm Hg, 70ºC).
and product XIX was isolated chromatographically,
eluent benzene. The obtained product was dried in a
vacuum (1 mm Hg, 70ºC). Yield 86%, oily substance.
1
Rf 0.80 (C). H NMR spectrum, δ, ppm: 1.13 m (36H,
3
3
CH3, JHH 7.2 Hz), 3.21 m (24H, CH2, JPH 11.7, 12.7
Hz), 6.84 s (3H, Ar). 31P NMR spectrum, δP, ppm: 74.1
(C6H6). Found, %: C 48.35; H 8.50; N 11.30; P 12.47.
M (m/z): 744.99. C30H63N6O3P3S3. Calculated, %: C
48.37; H 8.52; N 11.28; P 12.47. M 744.
Bis(2-thiono-2-(diethylamino)benzo[d][1,3,2]di-
1-(Tetraethyldiamidothionophosphoryloxy)-3,5-
diacetoxybenzene (XXIIIb). To 0.2 g of 1,3,5-triacet-
oxybenzene XXI dissolved in 5 ml of acetonitrile was
added 0.2 g of phosphorous hexaethyltriamide at
continuous stirring, at room temperature. After 2 days
0.025 g of sulfur was added and the stirring was
continued for another 2 days, the solvent was eva-
porated, and compound XXIIIb was isolated by
column chromatography, eluent benzene. The obtained
product was dried in a vacuum (1 mm Hg, 70ºC).
oxaphosphol-4-yl) diethylaminothionophosphate
1
(XVIIb), yield 26%, oily substance, Rf 0.37 (A). H
NMR spectrum, δ, ppm: 1.09 m, 1.17 m, 1.21 m (18H,
3
3
CH3, JHH 7.0 Hz), 3.20 m (4H, CH2, JPH 11.9 Hz),
3.26 m (4H, CH2, 3JPH 14.9 Hz), 3.50 m (4H, CH2, 3JPH
15.8 Hz), 6.85–6.94 m (4H, CH), 7.10 d (1H, CH),
7.12 d (1H, CH). 31P NMR spectrum, δP, ppm: 89.6,
70.2 (C6H6). Found, %: C 44.20; H 5.54; N 6.46; P
14.25. C24H36N3O6P3S3. M (m/z): 651.12 Calculated,
%: C 44.23; H 5.57; N 6.45; P 14.26. M 651.
1
Yield 63%, oily substance. Rf 0.75 (C). H NMR
spectrum, δ, ppm: 1.11 m (6H, CH3, 3JHH 6.9 Hz), 2.25
s (6H, CH3CO), 3.20 m (8H, CH2, 3JPH 12.4 Hz ), 6.72
d (1H, CH, 4JHH 1.2 Hz), 6.87 q (2H, CH, 4JHH 1.3 Hz).
13C NMR spectrum, δC, ppm: 13.7 s (CH3), 21.0 s
(CH3–C), 40.1 d (CH2), 111.0 s (1), 112.4 s (C3,5),
150.1 s (C2,6), 151.7 s (C4), 169.0 s [C (O)]. 31P NMR
spectrum, δP, ppm: 75.7 (CHCl3). Found, %: C 51.93;
H 7.11; N 6.58; P 7.45. C18H29N2O5PS. M (m/z):
416.76. Calculated, %: C 51.91; H 7.02; N 6.73; P
7.44. M 416.
Bis{2-thiono-2-(dimethylamino)benzo[d][1,3,2]di-
oxaphosphol-5-yl]} dimethylaminothionophosphate
1
(XVIIIa), yield 19%, oily substance, Rf 0.27 (A). H
3
NMR spectrum, δ, ppm: 2.86 g (12H, CH3, JPH
3
12.5 Hz), 2.96 d (6H, CH3, JPH 11.9 Hz), 6.80 d.d
(1H, CH, 3JHH 8.9 Hz, 4JHH 1.8 Hz), 6.84 d.d (1H, CH,
3JHH 7.9 Hz, 4JHH 1.2 Hz), 6.88–6.93 m (5H, CH), 7.00
d (1H, CH, 3JHH 8.9 Hz). 31P NMR spectrum, δP, ppm:
89.8, 68.5 (C6H6). Found, %: C 38.09; H 4.26; N, 7.40;
P 16.37. C18H24N3O6P3S3. Calculated, %: C 38.12; H
4.29; N 7.38; P 16.35.
1,3-Bis(tetraethyldiamidothionophosphoryloxy)-
5-acetoxybenzene (XXVb). To 0.2 g of compound
XXI dissolved in 5 ml of acetonitrile was added 0.4 g
of phosphorous hexaethyltriamide at continuous stir-
ring at room temperature. After 2 days was added
0.05 g of sulfur, and the stirring was continued for
another 2 days, the solvent was evaporated and
compound XXVb was isolated by column chromato-
graphy, eluent benzene. The obtained product was
dried in a vacuum (1 mm Hg, 70ºC). Yield 57%, oily
Bis{2-thiono-2-(diethylamino)benzo[d][1,3,2]di-
oxaphosphol-5-yl} diethylaminothionophosphate
1
(XVIIIb), yield 17%, oily substance, Rf 0.53 (A). H
NMR spectrum, δ, ppm: 0.86 m (6H, CH3), 1.17 m
(12H, CH3, 3JHH 6.1 Hz), 3.23 m (8H, CH2, 3JPH 15.6 Hz),
3
3.41 m (4H, CH2, JPH 14.3 Hz), 6.62 d (1H, CH),
3
6.83–6.91 m (3H, CH), 6.97 d (1H, CH, JHH 8.9 Hz),
3
7.00 d (1H, CH, JHH 8.9 Hz). 31P NMR spectrum, δP,
ppm: 88.4, 67.0 (C6H6). Found, %: C 44.21; H 5.50; N
6.43; P 14.24. C24H36N3O6P3S3. Calculated, %: C
44.23; H 5.57; N 6.45; P 14.26.
1
substance. Rf 0.64 (C). H NMR spectrum, δ, ppm:
3
1.12 m (24H, CH3, JHH 7.0 Hz), 2.26 s (3H, CH3CO),
3
3.20 m (16H, CH2, JPH 12.4 Hz ), 6.76 q (2H, CH,
4
4JHH 1.1 Hz), 6.95 d (1H, CH, JHH 1.5 Hz). 13C NMR
1,3,5-Tris(tetraethyldiamidothionophosphoryl-
oxy)benzene (XIX). To 0.2 g of phloroglucinol XVII
dissolved in 5 ml of acetonitrile was added 1.2 g of
phosphorous hexaethyltriamide at continuous stirring
and room temperature. After 45 min to the reaction
solution was added 0.05 g of sulfur, the stirring was
continued for another day, the solvent was evaporated,
spectrum, δC, ppm: 13.8 s (CH3), 21.2 s (CH3–C), 40.2
d (CH2), 110.9 s (C1,3), 112.2 s (C5), 152.0 s (C6),
154.1 s (C2,4), 169.0 s [C(O)]. 31P NMR spectrum, δP,
ppm: 76.5. (CHCl3). Found, %: C 49.67; H 7.95; N
9.63; P 10.60. C24H46N4O4P2S2. M (m/z): 580.24. Cal-
culated, %: C 49.64; H 7.98; N 9.65; P 10.67. M 580.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 6 2011

1090
RASADKINA et al.
substance. Rf 0.80 (C). 1NMR spectrum, δ, ppm: 0.91 s
1,3-Bis[ethoxy(diethylamido)thionophosphoryl-
a
3
oxy]-5-hydroxybenzene (XXVIII) and 1,3,5-tris-
[ethoxy(diethylamido)thionophosphatoxy]benzene
(XXIX). To 0,2 g of phloroglucinol XVII dissolved in
5 ml of dioxane at room temperature at continuous
stirring was added 0.88 g of ethyl diethylamidophos-
phite. A day latter to the reaction mixture 0.1 g of
sulfur was added, and the mixture was stirred for
another 4 days, the solvent was evaporated and the re-
sidue was chromatographed on a column eluting the ob-
tained product XXVIII or XXIX with benzene. The ob-
tained products were dried in a vacuum (1 mm Hg, 70ºC).
(6H, CH3e), 1.31 s (6H, CH3 ), 3.98 d.d (4H, CH2e, JPH
21.8 Hz, JHH 11.1 Hz), 4.27 d.d (4H, CH2a, JPH
21.1 Hz, 2JHH 11.1 Hz), 5.88 br.s (1H, OH), 6.63 s (2H,
CH), 6.69 s (1H, CH). 31P NMR spectrum, δP, ppm:
53.8 (CHCl3). Found, %: C 42.31; H 5.30; P 13.64.
C16H24O7P2S2. Calculated, %: C 42.29; H 5.32; P
13.63.
2
3
1,3,5-Tris(5,5-dimethyl-2-thiono-1,3,2-dioxaphos-
pharinan-2-yloxy)benzene (XXXII), yield 20%, mp
1
190–120ºC, Rf 0.54 (C). H NMR spectrum, δ, ppm:
0.92 s (9H, CH3e), 1.32 s (9H, CH3a), 3.99 d.d (6H, CH2e ,
3JPH 21.8 Hz, JHH 11.1 Hz), 4.28 d.d (6H, CH2a, JPH
2
3
1,3-Bis[ethoxy(diethylamido)thionophosphoryl]-
5-hydroxybenzene (XXVIII). Yield 85%, oily sub-
stance. Rf 0.55 (C). 1H NMR spectrum, δ, ppm: 1.12 m
22.3 Hz, JHH 11.1 Hz), 7.02 s (3H, CH). 31P NMR
2
spectrum, δP, ppm: 52.7 (CHCl3). Found, %: C 40.72;
H 5.35; P 15.05. C21O9H33P3S3. Calculated, %: C
40.77; H 5.38; P 15.02.
3
3
(12H, CH3, JHH 6.8 Hz), 1.32 m (6H, CH3–O, JHH
3
6.0 Hz), 3.28 m (8H, CH2–N, JPH 13.7 Hz), 4.11 m
(4H, CH2–O, 3JPH 18.8 Hz), 5.42 br.s (1H, OH), 6.15 s
(1H, CH), 6.29 s (2H, CH). 31P NMR spectrum, δP,
ppm: 71.6 (C6H6). Found, %: C 44.60; H 7.00; N 5.77;
P 12.70. C18H34N2O5P2S2. Calculated, %: C 44.62; H
7.07; N 5.78; P 12.78.
3,5-Bis(5,5-dimethyl-2-thiono-1,3,2-dioxaphos-
pharinan-2-yloxy)phenol (XXXI) and 3,5-bis(2-
thiono-1,3,2-dioxaphospharinan-2-yloxy)phenol
(XXXVII). To 1.6 mmol of compound XVII dissolved
in 5 ml of dioxane was added 0.32 g of triethylamine.
The resulting solution at cooling and continuous
stirrng was added dropwise to 1.6 mmol of 2-chloro-
1,3,2-dioxaphosphorinane XXXIII or 2-chloro-5,5-
dimethyl-1,3,2-dioxaphosphorinane XXXIV dissolved
in 3 ml of dioxane. The reaction mixture was kept at
room temperature for 1 h, then triethylamine hydro-
chloride was filtered off and to the solution was added
3.2 mmol of sulfur. After 15 days the solvent was
evaporated and the residue was chromatographed on a
column eluting the products XXXI, XXXVII with
benzene. The obtained products were dried in vacuum
(1 mm Hg, 70ºC).
1,3,5-Tris[ethoxy(diethylamido)thionophos-
phoryl]benzene (XXIX). Yield 12%, mp 115–116ºC,
1
Rf 0.72 (C). H NMR spectrum, δ, ppm: 1.08 m (18H,
3
3
CH3, JHH 7.3 Hz), 1.32 m (9H, CH3, JHH 7.4 Hz),
3
3.27 m (12H, CH2–N, JPH 13.3 Hz), 4.07 m (9N,
3
3
CH2–O, JPH 13.3 Hz, JHH 9.6 Hz), 6.53 s (3H, CH).
13C NMR spectrum, δC, ppm: 14.2 d (6C, CH3, JPС
3
3
8.7 Hz), 15.9 dd (3C, CH3, JPС 14.4 Hz), 40.4 g (6C,
2
2
CH2–N, J PС 3.9 Hz), 63.3 dd (2C, CH2–O, JPС
2
15.3 Hz), 105.3 s (3C, CH), 151.7 d (3C, C–O, JPС
6.7 Hz). 31P NMR spectrum, δP, ppm: 71.5 (C6H6). Found,
%: C 43.39; H 7.69; N 6.43; P 14.2. C24H48N3O6P3S3.
Calculated, %: C 43.43; H 7.29; N 6.33; P 14.00.
3,5-Bis(2-thiono-1,3,2-dioxaphospharinan-2-yl-
3,5-Bis(5,5-dimethyl-2-thiono-1,3,2-dioxaphos-
pharinan-2-yloxy)phenol (XXXI) and 1,3,5-tris(5,5-
dimethyl-2-thiono-1,3,2-dioxaphospharinan-2-yl-
oxy)benzene (XXXII). To 1.5 mmol of compound
XVII dissolved in 5 ml of dioxane was added 3.2 mmol
of compound XXX. The reaction was carried out at
50ºC at continuous stirring. After 15 days to the reac-
tion mixture3.2 mmol of sulfur was added, and the
mixture was further stirred for 7 days and the products
XXXI, XXXII were isolated by column chromato-
graphy, eluent benzene. The obtained products were
dried in a vacuum (1 mm Hg, 70ºC).
oxy)phenol (XXXVII), yield 75%, oily substance. Rf
1
0.31 (C). H NMR spectrum, δ, ppm: 1.86 d.d (2H,
CH2a, JHH 15.1 Hz), 2.24 d.d (2H, CH2a, 2JHH 15.1 Hz),
2
4.48 m (4H, OCH2e, 2JHH 12.9 Hz), 4.51 m (4H, OCH2a,
2JHH 12.9 Hz), 6.06 s (2H, CH), 6.12 s (1H, CH), 8.23
s (1H, OH). 13C NMR spectrum, δC, ppm: 26.1 s (2C,
CH2), 69.9 s (4C, OCH2), 99.2 s (3C, CH), 152.1 s
(1C, C–OH), 159.5 s (2C, C–OR). 31P NMR spectrum,
δP, ppm: 54.9 (DMSO). Found, %: C 43.50; H 6.18; P
14.14. C16H27O6P2S2. Calculated, %: C 43.53; H 6.16;
P 14.03.
Bis[3,5-bis(5,5-dimethyl-2-thiono-1,3,2-dioxa-
phospharinan-2-yl)phenyl] diethylamidophosphate
(XXXVIII). To 0.1 g of compound XXXI dissolved in
3,5-Bis(5,5-dimethyl-2-thiono-1,3,2-dioxaphos-
pharinan-2-yloxy)phenol (XXXI), yield 65%, oily
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 6 2011

PHOSPHORYLATION OF TRIHYDROXYBENZENES
1091
10. Nifant’ev, E.E., Maslennikova, V.I., Sotova, T.Yu.,
Vasyanina, L.K., and Shelenkova, L.V., Dokl. Akad.
Nauk, 2007, vol. 414, no. 3, p. 343.
5 ml of dioxane was added 0.064 ml of phosphorous
hexaethyltriamide at continuous constant stirring, at
room temperature. After keeping the solution for
15 days 0.0082 g of sulfur was added and the mixture
was stirred for 1 day. Then the solvent was evaporated
and the residue was chromatographed on a column
eluting compound XXXVIII with benzene. The
obtained product was dried in a vacuum (1 mm Hg,
11. Nifantyev, E.E., Maslennikova, V.I., and Merkulov, R.V.,
Acc. Chem. Res., 2005, vol. 38, no. 2, p. 108.
12. Slitikov, P.V., Bogoyavlenskii, V.A., Rasadkina, E.N.,
and Nifant’ev, E.E., Zh. Obshch. Khim., 2007, vol. 77,
no. 6, p. 938.
13. Malenkovskaya, M.A., Strebkova, E.V., Predvodite-
lev, D.A., and Nifant’ev, E.E., Zh. Obshch. Khim.,
2007, vol. 77, no. 3, p. 471.
14. Predvoditelev, D.A., Malenkovskaya, M.A., V’yun-
skovskaya, O.V., and Nifant’ev, E.E., Zh. Obshch.
Khim., 2008, vol. 78, no. 8, p. 1265.
15. Grachev, M.K., Kurochkina, G.I., Mishina, V.Yu.,
Mustafin, I.G., and Nifant’ev, E.E., Zh. Obshch. Khim.,
1999, vol. 69, no. 11, p. 1778.
1
70ºC). Yield 68%, oily substance, Rf 0.81 (C). H
3
NMR spectrum, δ, ppm: 1.18 m (6H, CH3CH2, JHH
9.2 Hz), 1.20 s (12H, CH3e), 1.31 s (12H, CH3a) 3.44 m
(4H, CH3CH2, JPH 14.2 Hz), 3.98 d.d (8H, CH2a, JPH
3
3
22.0 Hz, JHH 12.0 Hz), 4.28 d.d (8H, CH2a, JHH
11.1 Hz), 6.95 s (4H, CH), 7.06 s (2H, CH). 31P NMR
spectrum, δP, ppm: 53.2, 65.9 (CHCl3). Found, %: C
41.52; H 5.43; N 1.32; P 14.80. C36H56NO14P5S5.
Calculated, %: C 41.49; H 5.42; N 1.34; P 14.86.
2
2
16. Nifant’ev, E.E., Kukhareva, T.S., Soldatova, I.A., and
Chukbar, T.G., Zh. Obshch. Khim., 1986, vol. 56,
no. 12, p. 2487.
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