Phosphacyclophanes derived from hydroquinone and 4,4′-dihydroxybiphenyl

Article abstract of DOI:10.1023/A:1012357001662

The first representatives of linear phosphocyclophanes were prepared starting from hydroquinone or 4,4′-dihydroxybiphenyl and phosphorous triamides. The reaction course is influenced by the structures of the aromatic diol and alkyl substituents in the pho

Full text of DOI:10.1023/A:1012357001662

Russian Journal of General Chemistry, Vol. 71, No. 3, 2001, pp. 366 372. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 3, 2001,
pp. 401 408.
Original Russian Text Copyright
2001 by Nifant’ev, Rasadkina, Evdokimenkova.
Phosphacyclophanes Derived from Hydroquinone
and 4,4 -Dihydroxybiphenyl
E. E. Nifant’ev, E. N. Rasadkina, and Yu. B. Evdokimenkova
Moscow Pedagogical State University, Moscow, Russia
Received October 4, 2000
Abstract The first representatives of linear phosphocyclophanes were prepared starting from hydroquinone
or 4,4 -dihydroxybiphenyl and phosphorous triamides. The reaction course is influenced by the structures of
the aromatic diol and alkyl substituents in the phosphamide moiety. The phosphorus atom readily enters redox
reactions and complexation. The complexing power of the aromatic fragments of the synthesized molecules
is lower than that of classical p-cyclophanes.
We have shown previously that 1,5- and 2,7-di-
hydroxynaphthalenes readily react with equimolar
amounts of phosphorous triamides to give in high
yields the first representatives of double-deck systems,
p-cyclophanes [1].
and more complete phosphorylation, we used a molar
excess of hexaalkylphosphorous triamide, which after
reaction completion (1 mm) was removed in a
vacuum; after that, the residue was distilled (180
4
200 C, 10 mm). The final stage was cyclization
with an equivalent amount of hydroquinone. In the
course of the reaction, an oily product precipitated,
which was identified by spectroscopic methods as
cyclic bis(dialkylphosphoramidite) VIIa or VIIb
[scheme (1)].
Proceeding with this study, we have examined in
this work the reactions of phosphamides with hydro-
quinone and 4,4 -dihydroxybiphenyl. The goal of this
study was to prepare maximally symmetrical three-
dimensional molecular structures of the amidophos-
phite type. Two approaches were used: (a) molecular
assembling by bisphosphorylation of diols followed
by cyclization of the resulting products with diols and
(b) direct synthesis consisting in reaction of phos-
phamides with equimolar amounts of diols. It should
be noted that all phosphorylations were performed at
room temperature in anhydrous acetonitrile without
Note that the products behave differently depend-
ing on the substituent at phosphorus. Freshly prepared
sample with the NMe2 substituent (VIIa) dissolves in
methylene chloride, benzene, and dioxane. However,
after washing with acetonitrile and vacuum drying this
sample transforms into the form insoluble in the same
solvents. In methylene chloride the sample swells to
special removal of dialkylamine released in the reac- form a gel and dissolves only in DMF. Contrastingly,
tion. The reactions were performed under argon to
prevent oxidation.
compound VIIb with the NEt2 substituent is readily
soluble in all the above-mentioned solvents even after
reprecipitation and removal of solvents in a vacuum.
Both products are very unstable in air and change
color from light yellow to red. The 31P NMR spectra
of both cyclic compounds contain two singlets in the
characteristic phosphoramidite range with different
ratio of the integral intensities, which is probably due
In the synthesis of cyclic phosphites from hydroqui-
none I and phosphorous triamides IIa and IIb by path-
way a (similarly to the reaction with resorcinol [2]),
along with the bisphosphorylated products IIIa and
IIIb we obtained monophosphorylated compounds IVa
and IVb. These compounds exhibit different chroma-
tographic mobility and different chemical shifts in the
31P NMR spectra. Compounds IIIb and IVb were
characterized in the form of phosphorodiamidothioates
V and VI. On keeping the reaction mixture for 1 day,
the bisphosphorylation goes to completion, but in the
31P NMR spectra a weak signal of phosphoromono-
1
to stereoisomerism. The H NMR spectra were meas-
ured only for VIIb and were consistent with the pro-
posed structure.
Compounds VIIa and VIIb were prepared by meth-
od b at equimolar ratio of the reactants. In this case
the physicochemical characteristics of the products
agreed with those of the compounds prepared by
method a. However, method b is preferable because
of shorter reaction time.
amidite is observed ( 140.0 ppm), which, as will be
P
shown below, is due to formation of the cyclic prod-
uct. To suppress the side process and ensure faster
1070-3632/01/7103-0366$25.00 2001 MAIK Nauka/Interperiodica

PHOSPHACYCLOPHANES DERIVED FROM HYDROQUINONE
367
Scheme 1.
HO
P(NR2)2
(R2N)2P
S
P(NR2)2
S
S
V
VI
S
S
a. 1:2
HO
P(NR2)2
IVa, IVb
(R2N)2P
P(NR2)2
+
IIIa, IIIb
HO
OH + P(NR2)3
I
I
O
O
b. 1:1
R2NP
PNR2
O
O
VIIa, VIIb
R = Me (a), Et (b).
Cyclic bis(dialkylphosphoramidites) VIIa and
VIIb readily add oxygen and sulfur [Scheme (2)]:
0.5 ppm, which suggests preservation of stereoiso-
merism.
Scheme 2.
Replacement of one hydroxy group in hydroqui-
none by the p-phenoxy group affects both the course
of phosphorylation and the properties of the resulting
products.
O
O
O
O
O
[O]
R2NP
O
VIIa, VIIb
PNR2
The NMe2 derivative IIa readily (within 5 min)
phosphorylates 4,4 -dihydroxybiphenyl [Scheme (3)].
However, isolation of product XI is difficult, because
it immediately starts to disproportionate to form cyclic
bis(phoshoramidite) XIII. Addition of sulfur to the
reaction solution allows isolation of bis(phosphorodi-
amidothioate) XII, which precipitates as a colorless
powder readily soluble in methylene chloride. If a
solution of 1 mol of X is added 5 min after the start of
the reaction, a white powder precipitates, which is
limitedly soluble in acetonitrile and methylene chlo-
ride (the solubility is sufficient to record the 31P NMR
spectrum) and insoluble even in such polar solvents
VIIIa, VIIIb
S
O
O
O
O
S
R2NP
S
VIIa, VIIb
PNR2
IXa, IXb
R = Me (a), Et (b).
as DMF and DMSO. According to the spectra (
P
The resulting cyclic bis(phosphoroamidates) VIIIa
and VIIIb and -amidothioates IXa and IXb are pow-
dered substances; similar to [3, 4], their melting point
decreases and the solubility increases in going from
the NMe2 to NEt2 derivatives. Phosphorothioates IXa
and IXb were isolated by column chromatography,
and phosphates VIIIa and VIIIb, by chromatography
and recrystallization from acetonitrile. The 31P NMR
spectra of all these compounds contain two singlets
each, with their chemical shifts differing by 0.2
140 ppm) and taking into account our previous results,
the reaction product can be identified as cyclic bis-
(phosphoramidite) XIII.
This compound is also formed at equimolar ratio of
reactants in one stage. The reaction starts very actively
but is complete only in 1 day, as indicated by the
31P NMR spectrum.
Bisphosphorylation of diol X with amide IIb is
complete in 1.5 h. Phosphorodiamidite XIV is fairly
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 3 2001

368
NIFANT’EV et al.
Scheme 3.
(Me2N)2PO
S
OP(NMe2)2
S
XII
S
1:2
(Me2N)2PO
OP(NMe2)2
XI
X or XI
P(NMe2)3 + HO
OH
X
O
O
O
O
1:1
Me2NP
PNMe2
XIII
stable and disproportionates to form cyclic bis(phos-
phoramidite) XVI only on heating (e.g., at attempted
in the form of phosphorodiamidothioate XV. Both
product XIV containing P3+ and phosphorothioate XV
high-vacuum distillation); it was fully characterized are oily substances readily soluble in organic solvents.
Scheme 4.
(Et2N)2PO
S
OP(NEt2)2
S
XV
S
1:2
(Et2N)2PO
OP(NEt2)2
XIV
X
IIb + X
O
O
O
1:1
Et2NP
PNEt2
O
XVI
Addition of 1 mol of diol to XIV or single-stage
synthesis at the molar ratio IIb : X = 1 : 1 yields a
colorless powder of XVI, which precipitates from the
reaction solution. In contrast to XIII, it is readily
soluble in methylene chloride and less soluble in ben-
zene and dioxane. Its 31P NMR spectrum contains a
singlet in the range typical of phosphoramidites, and
1
the H NMR spectrum contains two doublets in the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 3 2001

PHOSPHACYCLOPHANES DERIVED FROM HYDROQUINONE
369
range of aromatic protons and signals from the NEt2
protons. We believe that the different physicochemical
properties of XIII and XVI are due to their structural
features.
tography and reprecipitation, respectively [Scheme (5)].
These compounds are high-melting powders readily
soluble in chlorinated solvents. Their 31P NMR spec-
tra contain singlets in the ranges typical of phosphor-
amidates and phosphoramidothioates; the retention
factors of XVII and XVIII differed considerably from
By addition of sulfur and oxidation, compound
XVI was converted to thio and oxo derivatives XVII
and XVIII, which were purified by column chroma-
1
each other and from that of XVI, whereas the H
NMR spectra of all the three substances were similar.
Scheme 5.
S
S
P(NEt2)2
(Et2N)2P
S
XVII
XVI
O
O
[O]
Et2NP
O
PNEt2
O
O
XVIII
The complexing power of the phosphorus atom
was evaluated in reactions of acetylacetonatodicarbo-
nylrhodium(I) with compounds VIIb and XVI and of
Mo(CO)6 with phenol derivative X. Rhodium com-
plexes XIX and XX were prepared at room tempera-
ture in methylene chloride and purified by reprecipita-
tion; their 31P NMR spectra showed splitting with the
direct coupling constants P Rh typical of square
planar Rh(I) complexes, and the IR spectra contained
the OC Rh absorption band at about 1990 cm .
Molybdenum complex XXI was prepared in dioxane
1
(reactant concentrations 0.12 M) at 95 C:
Scheme 6.
(CO)5Mo
Et2N
O
O
O
NEt2
Mo(CO)6
XVI
P
P
O
Mo(CO)5
XXI
It is interesting that in the course of the reaction
even at 70 C a colorless gel started to form in the
reaction solution, and at 95 C this gel occupied prac-
tically the whole reaction volume. After separation of
the gel we found that the molybdenum complex was
present in the solution. It was isolated in a 34% yield
and fully characterized. Its 31P NMR spectrum con-
tained a singlet in the range typical of monosubsti-
tuted molybdenum phosphite complexes. The dried
gel was a powdered substance insoluble in organic
solvents; it could be a polymer formed in the presence
of the molybdenum carbonyl complex.
We also attempted to perform complexation reac-
tions involving the aromatic fragments. We started
from cyclic phosphates VIIIb and XVIII, picric acid,
and Cr(CO)6. The expected complexes did not form.
We believe that the phosphorus and oxygen atoms
decrease the electron density in the aromatic rings,
which decreases their capability to form charge-trans-
fer complexes typical of p-cyclophanes [5 7].
Thus, introduction of oxygen and phosphorus
atoms into p-cyclophane molecules strongly affects
their complexing power; however, the presence of
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370
NIFANT’EV et al.
trivalent phosphorus allows preparation of another
type of complexes, which may be promising as cata-
lysts and drug carriers.
2 h, 0.6 g of sulfur was added, and the mixture was
stirred for an additional 2 h at room temperature. The
solution was filtered, the solvent was vacuum-evap-
orated, and the residue was purified by column chro-
matography (eluent benzene).
EXPERIMENTAL
1,4-Phenylene bis(tetraethylphosphorodiamido-
The IR spectra of XIX and XX were measured on
thioate-O) V. Yield 1.25 g (34%), mp 111 112 C,
a Specord IR-75 spectrometer in methylene chloride
1
1
1
Rf 0.87 (E). H NMR spectrum, , ppm: 1.17 t (12H,
in the range 4000 400 cm . The H NMR spectra of
IIIa, IIIb, VIIIa, VIIIb, IXa, XII, and XVII XXI in
CDCl3 and of VIIb and XVI in C6D6 were measured
on a Bruker WH-250 spectrometer(250 MHz) relative
to TMS, and those of V, VI, IXb, and XIV in CDCl3,
on a Bruker AC-200 spectrometer (200 MHz). The
31P NMR spectra of VIIb, IXa, IXb, XVI, XVII, and
XXI in benzene, VIIa IXa, VIIb IXb, XII XIV,
and XVI XX in methylene chloride, and IIIa, IIIb,
V, and VI in acetonitrile were measure on a Bruker
WP-80SY spectrometer at 32.4 MHz relative to 85%
H3PO4.
Me), 3.22 m (8H, CH2), 7.1 (4H, CH). 31P NMR
spectrum:
76.8 ppm. Found, %: C 49.42; H 5.69;
N 10.81; PP 12.54. C22H44N4O2P2S2. Calculated, %:
C 50.57; H 8.43; N 10.72; P 11.88.
4-Hydroxyphenyl tetraethylphosphorodiamido-
thioate-O VI. Yield 0.978 g (40%), mp 110 111 C,
1
Rf 0.76 (E). H NMR spectrum, , ppm: 1.13 t (12H,
Me), 3.2 m (8H, CH2), 6.2 s (1H, OH), 6.71 d (2H,
CH), 6.91 d (2H, CH). 31P NMR spectrum:
P
76.7 ppm. Found, %: C 53.21; H 7.74; N 8.92; P
9.62. C14H25N2O2PS. Calculated, %: C 53.15; H
7.97; N 8.86; P 9.79.
The TLC analysis was performed on Silufol plates
with the eluent systems benzene dioxane, 5 : 1 (A),
10 : 1 (B), chloroform methanol, 5 : 1 (C), and hex-
ane dioxane, 5 : 1 (D), 3 : 1 (E). The chromatograms
were developed by exposure to iodine vapor, calcina-
tion, and treatment with 1% aqueous AgNO3. Adsorp-
tion chromatography was performed in a column
packed with silica gel L100/160.
Cyclobis(1,4-phenylene dialkylphosphoramidi-
tes) VIIa and VIIb. To a solution of 1.4 mmol of
IIIa or IIIb in 10 ml of acetonitrile was added
1.4 mmol of hydroquinone. The mixture was stirred
for 4 h at room temperature. The next day the solution
was decanted from the oily product formed on the
bottom, and the residue was washed with acetonitrile
and vacuumdried (3 h, 50 C, 1 mm).
1,4-Phenylene bis(tetraalkylphosphorodiamidi-
tes) IIIa and IIIb. To a solution of 67 mmol of
hydroquinone in 30 ml of acetonitrile was added
21 mmol of hexaalkylphosphorous triamide, and the
mixture was left for 24 h at room temperature. The
solvent and excess triamide were distilled off in a
vacuum, and the residue was distilled [bath tempera-
Cyclobis(1,4-phenylene dimethylphosphorami-
dite) VIIa. Yield 42%, Rf 0.8 (A). 31P NMR spectrum:
140.03, 140.21 ppm. Found, %: C 52.51; H 5.68;
N 7.42; P 16.68. C16H20N2O4P2. Calculated, %: C
52.46; H 5.50; N 7.65; P 16.94.
P
4
ture 140 180 C (IIIa), 180 200 C (IIIb), 10 mm].
Cyclobis(1,4-phenylene diethylphosphoramidite)
1
VIIb. Yield 60%, Rf 0.78 (A), 0.62 (B). H NMR
1,4-Phenylene bis(tetramethylphosphorodiami-
1
3
dite) IIIa. Yield 40%, Rf 0.3 (A). H NMR spectrum,
spectrum, , ppm: 0.91 t (12H, Me, JHH 6.4 Hz),
3
3.1 m (8H, CH2, JPH 9.82 Hz), 7.16 s (8H, CH). 31P
, ppm: 1.08 d (24H, Me), 7.01 s (4H, CH). 31P NMR
NMR spectrum:
142.46, 142.55 ppm (CH2Cl2),
spectrum:
136.7 ppm. Found, %: C 48.46; H 8.39;
P
P
141.8, 142.04 ppm (C6H6). Found P, %: 14.21.
C20H28N2O4P2. Calculated P, %: 14.69.
N 16.03; P 17.53. C14H28N4O2P2. Calculated, %:
C 48.54; H 8.15; N 16.17; P 17.92.
Cyclobis(1,4-phenylene dialkylphosphorami-
dates) VIIIa and VIIIb. To a solution of 0.45 mmol
of cyclic phosphoramidite VIIa or VIIb in 15 ml of
methylene chloride was added 0.9 mmol of the com-
plex H2O2(NH2)2CO. The mixture was stirred for 2 h
at room temperature. The solution was filtered, the
solvent was vacuum-distilled, and the residue was re-
1,4-Phenylene bis(tetraethylphosphorodiami-
dite) IIIb. Yield 52%, Rf 0.8 (A). H NMR spectrum,
1
, ppm: 1.08 t (24H, Me), 3.12 m (16H, CH2), 6.91 s
(4H, CH). 31P NMR spectrum:
133 ppm. Found P,
P
%: 13.50. C22H44N4O2P2. Calculated P, %: 13.54.
1,4-Phenylene bis(tetraethylphosphorodiamido-
thioate-O) V and 4-hydroxyphenyl tetraethylphos- crystallized from acetonitrile (VIIIa) or purified by
phorodiamidothioate-O VI. A solution of a mixture
of 1 g of hydroquinone and 5.6 g of hexaethylphosphor-
ous triamide in 20 ml of acetonitrile was stirred for
column chromatography, elution with chloroform
methanol, 10 : 1 (VIIIb). The phosphates were
vacuum-dried for 2.5 h (70 C, 1 mm).
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PHOSPHACYCLOPHANES DERIVED FROM HYDROQUINONE
371
3
3
Cyclobis(1,4-phenylene dimethylphosphorami-
Me, JPH 12.37 Hz), 7.05 d (4H, CH, JHH 8.96,
3
date) VIIIa. Yield 86%, mp 80 82 C, Rf 0.56 (C).
4JHH 1.71 Hz), 7.47 d (4H, CH, JHH 8.11 Hz). 31P
NMR spectrum:
H 6.39; N 11.43; P 12.89. C20H32N4O2P2S2. Calcu-
lated, %: C 49.37; H 6.63; N 11.52; P 12.73.
3
1H NMR spectrum, , ppm: 2.68 d (12H, Me, JHH
81.2 ppm. Found, %: C 49.41;
P
7.26 Hz), 7.26 s (8H, CH). 31P NMR spectrum:
1.81, 2.2 ppm. Found, %: C 48.32; H 4.95; N 7.12P;
P 15.64. C16H20N2O6P2. Calculated, %: C 48.25;
H 5.06; N 7.04; P 15.55.
Cyclobis(biphenyl-4,4 -diyl dimethylphosphor-
amidite) XIII. To a solution of 0.321 g of 4,4 -dihy-
droxybiphenyl in 10 ml of acetonitrile was added
0.282 g of hexamethylphosphorous triamide, and the
mixture was stirred at room temperature for 4 h. The
resulting colorless precipitate was filtered off, washed
with acetonitrile, and vacuum-dried (3 h, 50 C, 1 mm
Hg). Yield 0.351 g (78%), mp 153 155 C, Rf 0.86
Cyclobis(1,4-phenylene diethylphosphorami-
date) VIIIb. Yield 91%, mp 70 72 C, Rf 0.60 (C).
3
1H NMR spectrum, , ppm: 1.02 t (12H, Me, JHH
3
6.83 Hz), 3.18 m (8H, CH2, JPH 11.95 Hz), 7.18 s
(8H, CH). 31P NMR spectrum:
1.21, 1.34 ppm
P
(CH2Cl2). Found P, %: 13.71. C20H28N2O6P2. Calcu-
lated P, %: 13.63.
(B). 31P NMR spectrum:
140.3 ppm. Found, %:
P
C 66.78; H 6.25; N 4.98; P 10.64. C28H28N2O4P2.
Calculated, %: C 66.89; H 6.32; N 4.88; P 10.78.
Cyclobis(1,4-phenylene dialkylphosphoramido-
thioates-O,O ) IXa and IXb. To a solution of
1.2 mmol of cyclic phosphoramidite VIIa or VIIb in
10 ml of methylene chloride was added 2.4 mmol of
sulfur, and the mixture was stirred for 2.5 h at room
temperature. The solution was filtered and vacuum-
evaporated, and the residue was purified by column
chromatography, eluent benzene dioxane, 10 : 1.
Products IXa and IXb were vacuum-dried (2.5 h,
60 C, 1 mm).
Biphenyl-4,4 -diyl bis(tetraethylphosphorodi-
amidothioate-O) XIV. To a solution of 0.161 g of
4,4 -dihydroxybiphenyl in 10 ml of acetonitrile was
added 0.43 g of hexaethylphosphorous triamide. The
mixture was stirred for 100 min at room temperature,
after which 0.06 g of sulfur was added, and the mix-
ture was stirred for an additional 2 h at room tempera-
ture. The solution was filtered to remove excess sulfur
and vacuum-evaporated; the residue was purified by
column chromatography, elution with benzene. Com-
pound XV (yellow oil) was vacuum-dried (2.5 h,
60 C, 1 mm). Yield 0.41 g (69%), Rf 0.61 (B).
Cyclobis(1,4-phenylene dimethylphosphorami-
dothioate-O,O ) IXa. Yield 49%, mp 72 73 C, Rf
1
0.37 (A). H NMR spectrum, , ppm: 2.95 d (12H,
Me), 7.16 s (8H, CH). 31P NMR spectrum:
68.80,
1H NMR spectrum, , ppm: 1.16 t (24H, Me), 3.25 m
P
(16H, CH2), 7.18 d (4H, CH), 7.48 d (4H, CH). 31P
69.45 ppm (CH2Cl2), 68.28, 68.89 ppm (C6H6).
Found, %: C 44.76; H 4.59; N 6.46; P 14.26.
C16H20N2O4P2S2. Calculated, %: C 44.64; H 4.68;
N 6.51; P 14.39.
NMR spectrum:
76.1 ppm. Found P, %: 10.44.
P
C28H48N4O2P2S2. Calculated P, %: 10.35.
Cyclobis(biphenyl-4,4 -diyl diethylphosphorami-
dite) XVI. To a solution of 0.18 g of 4,4 -dihydroxy-
biphenyl in 10 ml of acetonitrile was added 0.24 g
of hexaethylphosphorous triamide. The mixture was
stirred for 4 h at room temperature. After 20 h the
solution was partially evaporated, and the colorless
precipitate that formed was filtered off, washed with
acetonitrile, and vacuum-dried (3 h, 50 C, 1 mm).
Cyclobis(1,4-phenylene diethylphosphoramido-
thioate-O,O ) IXb. Yield 49%, mp 62 63 C, Rf 0.72
1
(A), 0.52 (B). H NMR spectrum, , ppm: 1.12 t
(12H, Me), 3.39 m (8H, CH2), 7.15 s (8H, CH). 31P
NMR spectrum:
68.1, 68.63 ppm (CH2Cl2), 67.73,
P
68.36 ppm (C6H6). Found P, %: 12.54. C20H28N2O4
P2S2. Calculated P, %: P 12.76.
1
Yield 0.149 g (84%), mp 89 90 C, Rf 0.76 (B). H
Biphenyl-4,4 -diyl bis(tetramethylphosphorodi-
amidothioate-O) XII. To a solution of 0.121 g of
4,4 -dihydroxybiphenyl in 10 ml of acetonitrile was
added 0.212 g of hexamethylphosphorus triamide. The
solution was stirred for 5 min at room temperature,
after which 0.041 g of sulfur was added, and the mix-
ture was stirred for an additional 2 h at room tempera-
ture. The resulting precipitate was filtered off, washed
with acetonitrile, and vacuum-dried (2.5 h, 60 C,
1 mm Hg). Yield of the colorless crystalline com-
pound 0.188 g (62%), mp 216 218 C, Rf 0.60 (B),
NMR spectrum, , ppm: 0.92 t (12H, Me), 3.14 m
3
(8H, CH2), 7.19 d (8H, CH, JHH 8.11 Hz), 7.29 d
3
(8H, CH, JHH 8.53 Hz). 31P NMR spectrum:
141.5 ppm. Found P, %: 10.65. C32H36N2O4P2. CalP-
culated P, %: P 10.78.
Cyclobis(biphenyl-4,4 -diyl diethylphosphorami-
dothioate-O,O ) XVII. To a solution of 0.196 g of
XVI in 5 ml of methylene chloride was added 0.022 g
of sulfur. The mixture was stirred for 1.5 h at room
temperature. The solution was filtered, the solvent
was removed in a vacuum, and the residue was puri-
1
0.32 (D). H NMR spectrum, , ppm: 2.66 d (24H,
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372
NIFANT’EV et al.
fied by column chromatography, eluent benzene
dioxane, 10 : 1. The product XVII was vacuum-dried
(2.5 h, 60 C, 1 mm). Yield 0.15 g (69%), mp
3JPH 11.95 Hz), 5.33 s (H, CH-acac), 7.28 d (8H, CH,
3
3JHH 8.11 Hz), 7.41 d (8H, CH, JHH 8.54 Hz). 31P
NMR spectrum:
133.72 ppm (JPRh 260.98 Hz).
P
1
208 209 C, Rf 0.51 (B). H NMR spectrum, , ppm
Found, %: C 51.20; H 4.79; N 2.58. C44H50N2O10
P2Rh2. Calculated, %: C 51.08; H 4.87; N 2.71.
(CDCl3): 1.11 t (12H, Me), 3.41 m (8H, CH2), 7.27 d
3
3
(8H, CH, JHH 7.24 Hz), 7.50 d (8H, CH, JHH
8.54 Hz). 31P NMR spectrum: P 67.44 ppm (CH2Cl2),
66.93 ppm (C6H6). Found, %: C 6.03; H 5.64; N 4.23.
C32H36N2O4P2S2. Calculated, %: C 60.17; H 5.68;
N 4.39.
-[Cyclobis(biphenyl-4,4 -diyl diethylphosphor-
amidite)]bis[pentacarbonylmolybdenum(0)] XXI.
To a solution of 0.104 g of XVI in 2 ml of benzene
was added 0.095 g of Mo(CO)6, and the mixture was
heated for 8 h in a sealed ampule at 95 C. The solu-
tion was decanted, the solvent was distilled off in a
vacuum, and the residue was washed with acetonitrile
and vacuum-dried (5 h, 50 C, 1 mm). Yield
0.064 g (34%), decomposition point 132 135 C, Rf
Cyclobis(biphenyl-4,4 -diyl diethylphosphorami-
date) XVIII. To a solution of 0.156 g of XVI in 10 ml
of methylene chloride was added 0.051 g of H2O2
(NH2)2CO, and the mixture was stirred at room tem-
perature for 2 h. The solution was filtered off, the
solvent was distilled off in a vacuum, and the residue
was recrystallized from acetonitrile and vacuum-dried
(2.5 h, 70 C, 1 mm Hg), yield 0.15 g (91%), mp 206
1
0.75 (A). H NMR spectrum, , ppm: 1.2 t (12H, Me,
3JHH 7.15 Hz), 3.42 m (8H, CH2), 7.26 d (8H, CH,
3
3JHH 8.25 Hz), 7.54 d (8H, CH, JHH 8.25 Hz). 31P
NMR spectrum:
164.6 ppm. Found, %: C 48.26;
P
1
H 3.61; N 2.64. C42H36Mo2N2O14P2. Calculated, %:
C 48.19; H 3.47; N 2.68.
207 C, Rf 0.60 (C). H NMR spectrum, , ppm: 1.02 t
3
3
(12H, Me, JHH 7.26 Hz), 3.20 m (8H, CH2, JPH
3
12.1 Hz), 7.23 d (8H, CH, JHH 8.25 Hz), 7.43 d (8H,
CH, JHH 8.79 Hz). 31P NMR spectrum:
1.41 ppm
3
ACKNOWLEDGMENTS
(CH2Cl2). Found P, %: 10.09. C32H36N2OP6P2. Calcu-
lated P, %: 10.21.
The study was financially supported by the Basic
Natural Science Foundation (St. Petersburg) and by
the Russian Universities Basic Research program
(project no. 2211).
-[Cyclobis(1,4-phenylene diethylphosphorami-
dite)]bis[acetylacetonatocarbonylrhodium(I)] XIX.
A solution of 0.056 g of VIIb in 3 ml of methylene
chloride was added dropwise to a solution of 0.068 g
of Rh(acac)(CO)2 in 3 ml of methylene chloride. The
mixture was left for 24 h at room temperature. Com-
pound XIX was reprecipitated from hexane, filtered,
and vacuum-dried for 2 h (40 C, 1 mm). Yield
0.872 g (84%), decomposition point 164 167 C, Rf
REFERENCES
1. Nifant’ev, E.E., Rasadkina, E.N., Evdokimenko-
va, Yu.B., Vasyanina, L.K., Stash, A.I., and Bel’-
skii, V.K., Zh. Obshch. Khim., 2001, vol. 71, no. 2,
pp. 203 211.
1
0.48 (C). IR spectrum, , cm : 1990 (CO Rh), 1510,
2. Nifant’ev, E.E., Rasadkina, E.N., and Yankovich, I.V.,
1
1570 (acac). H NMR spectrum, , ppm: 1.08 t (12H,
Zh. Obshch. Khim., 1997, vol. 67, no. 11, pp. 1812 1817.
3
Me, JHH 11.55 Hz), 1.66 s (3H, Me-acac), 2.01 s
3. Nifantyev, E.E., Rasadkina, E.N., Yankovich, I.V.,
Vasyanina, L.K., Belsky, V.K., and Stash, A.I., Hetero-
atom Chem., 1998, vol. 9, no. 7, pp. 643 649.
(3H, Me-acac), 3.51 m (8H, CH2), 5.38 s (H, CH-
acac) 7.19 s (8H, CH). 31P NMR spectrum:
P
134.4 ppm (JPRh 261.22 Hz). Found P, %: 7.91.
C32H42N2O10P2Rh2. Calculated P, %: 7.88.
4. Nifant’ev, E.E., Rasadkina, E.N., Yankovich, I.V.,
Bel’skii, V.K., and Stash, A.I., Zh. Obshch. Khim.,
1999, vol. 69, no. 1, pp. 36 42.
-[Cyclobis(biphenyl-4,4 -diyl diethylphosphor-
amidite)]bis[acetylacetonatocarbonylrhodium(I)]
XX. A solution of 0.076 g of XIIIb in 3 ml of me-
thylene chloride was added dropwise to a solution of
0.068 g of Rh(acac)(CO)2 in 3 ml of methylene
chloride. The mixture was left for 24 h at room tem-
perature. Compound XX was reprecipitated from
hexane, filtered, and vacuum-dried for 2 h (40 C,
1 mm). Yield 0.128 g (94%), decomposition point
5. Sternhell, S., Tansey, C.W., Tobe, Y., and Koribo, K.,
Magn. Reson. Chem., 1990, vol. 28, no. 10, pp. 902
907.
6. Mori, K., Odashina, K., Itail, A., Iilaka, Y., and Ko-
da, K., Heterocycles, 1984, vol. 12, no. 12, pp. 902
907.
1
175 177 C, Rf 0.62 (C). IR spectrum, , cm : 1990
7. Sergeeva, E.V., Rozenberg, E.V., Vorontsova, V.V.,
Mikul’shina, V.V., Vorontsova, N.V., Smirnov, A.V.,
Dolgushin, F.M., and Yanovskii, A.I., Izv. Ross. Akad.
Nauk, Ser. Khim., 1998, no. 1, pp. 142 150.
1
(CO Rh), 1510, 1570 (acac). H NMR spectrum, ,
3
ppm: 1.09 t (12H, Me, JHH 7.01 Hz), 1.51 s (3H,
Me-acac), 1.96 s (3H, Me-acac), 3.57 m (8H, CH2,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 3 2001