Macrocyclic systems on the basis of phosphorus acids and 2,7-dihydroxynaphthalene

Article abstract of DOI:10.1023/B:RUGC.0000007643.79978.ad

Syntheses of macrocyclic systems containing three 2,7-dihydroxynaphthalene residues and three residues of thiophosphoric and phosphorous amides in various ratios are developed. Chemical properties of the obtained compounds are studied.

Full text of DOI:10.1023/B:RUGC.0000007643.79978.ad

Russian Journal of General Chemistry, Vol. 73, No. 8, 2003, pp. 1208 1212. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 8, 2003,
pp. 1279 1283.
Original Russian Text Copyright
2003 by Rasadkina, Slitikov, Evdokimenkova, Nifant’ev.
Macrocyclic Systems on the Basis of Phosphorus Acids
and 2,7-Dihydroxynaphthalene
E. N. Rasadkina, P. V. Slitikov, Yu. B. Evdokimenkova, and E. E. Nifant’ev
Moscow State Pedagogical University, Moscow, Russia
Received October 9, 2001
Abstract Syntheses of macrocyclic systems containing three 2,7-dihydroxynaphthalene residues and three
residues of thiophosphoric and phosphorous amides in various ratios are developed. Chemical properties of the
obtained compounds are studied.
We earlier prepared [1] on the basis of dihydroxy-
naphthalenes first representatives of biscyclophos-
phoramidites whose molecules contain regular comb-
inations of two aromatic fragments and two phos-
phorous amide I residues. In the present work we set
our selves the task to prepare analogous macrocyclic
compounds with a larger molecular cavity. Systems
whose molecules contain three 2,7-dihydroxynaph
thalene (II) and phosphorus acid residues were chosen
as target compounds. During these investigations we
made use of our experience in designing analogous
but simpler macrorings on the basis of resorcinol and
hexaalkylphosphorous triamides [2]. First we intended
to prepare the target macrorings by the molecular
assembly method that consists in consecutive binding
naphthyl and phosphorous amide fragments. However,
one this way we faced difficulties associated with the
tendency of the intermediate linear oligonaphthylene
phosphoroamidites for disproportionation leading to
formation of biscyclophosphoramidites. Therefore, we
O
O
O
O
P NEt2
Et N P
2
I + IV +
VI
2II
CH3CN
P(NEt2)3 +
2HNR2
OP(NEt2)2
OH
(Et2N)2PO
HO
OH
O
Ib
II
III
3.5II
O
HO
O
O
O
P
P
P
P
NEt2
NEt2
IV
S
O
OH
HO
O
S
O
S
NEt2
NEt2
V
1070-3632/03/7308-1208$25.00 2003 MAIK Nauka/Interperiodica

MACROCYCLIC SYSTEMS ON THE BASIS OF PHOSPHORUS ACIDS
1209
have modified this scheme and, to enhance stability
of linear intermediates, introduced the stage of their
conversion into thiophosphates.
with hexaethylphosphorous triamide (Ib). With hexa-
methylphosphorous triamide (Ia), an extremely fast
disproportionation of linear triphosphite was observed,
which prevented its preparative conversion to thio-
phosphate V.
With this additional stage, we have accomplished
two variants of assembly of the target systems.
Thiophosphate V was isolated by column chro-
The first variant involved using tetraethylphos-
phorodiamidite III derived from 2,7-dihydroxynaph-
thalene [1]. This compound was reacted with 2,7-di-
hydroxynaphthalene to obtain diol IV which was im-
mediately stabilized as disulfate V. Note that the
target product IV was almost quantitatively formed
only with excess diol II. With equimolar reagent
amounts, the major product was biscyclophosphoro-
amidite VI. Note that a linear oligomer containing
three aromatic fragments IV could only be prepared
matography as an oil. Its 31P NMR spectrum con-
tained a singlet at
67.30 ppm, characteristic of
P
1
monoamidothiophosphates. In the H NMR spectrum,
signals of all proton groups were observed, including
that of two hydroxy groups with an expected integral
intensity ratio.
Further on phosphocyclization of compound V
with with 1 mol of hexaalkylphosphorous triamide Ia
or Ib was performed.
S
P
P
O
O
O
O
R2N
R2N
CH3CN
V + Ia, Ib
HNR2
S
O
S
O
S
S
S
P
P
O
O
P
P
O
O
O
O
Et2N
Et2N
NEt2
NEt2
VIIa, VIIb
R = Me (VIIa, VIIIa), Et (VIIb, VIIIb).
VIIIa, VIIIb
Products VIIa, VIIb were viscous oils. Their 31P
amidothiophosphates. Note an interesting feature of
the H NMR spectra: When the system contained dif-
ferent alkyl substituents on nitrogen, nonequivalence
of all proton groups was observed, whereas in the case
of the same substituents on nitrogen, such a non-
equivalence was lacking.
1
NMR spectra contained two singlets at
139.70 and
66.67 (VIIa) and 140.70 and 66.67 ppmP(VIIb) with
an integral intensity ratio of 1:2. These compounds
readily disproportionated on handling, and, therefore,
they were stabilized by sulfurization. After purifica-
tion by column chromatography, thiophosphates
VIIIa, VIIIb were obtained as low-melting powders.
The 31P NMR spectrum of compound VIIIa contained
two signals at P 68.13 and 66.67 ppm (1:2), whereas
the spectrum of ethyl derivative VIIIb, one singlet at
The second variant involved synthesis of di-
naphthyl phosphoramidites IXa, IXb and their sub-
sequent phosphocyclization with phosphorylated diols
IIIa, IIIb.
66.67 ppm; these signals all are characterisic of
P
S
CH3CN
Ia, Ib + 2.5II
2HNR
HO
O
O
OH
HO
O
O
OH
P
P
S
NEt2
NEt2
IXa, IXb
R = Me (IXa, Xa), Et (IXb, Xb).
Xa, Xb
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 8 2003

1210
RASADKINA et al.
1
It was shown that using excess diol II in the
and 66.88 ppm (Xb). The H NMR spectra of Xa,
Xb were identical to those of IXa, IXb.
synthesis of compounds IXa, IXb completely ex-
cludes formation of cyclic products. However, in this
case, chromatographic isolation of IXa, IXb is re-
quired, which sharply decreases their yield. For this
reason, we converted crude phosphoramidites IXa,
IXb into thiophosphates Xa, Xb. These latter were
isolated pure in high yields and completely charac-
terized. Their 31P NMR spectra contained signals
For the subsequent cyclization, thiophosphates Xa,
Xb were added to phosphorylated diol IIIb, more
specifically, to a mixture of amide Ib and diol II ten
minutes after phosphorylation had began (using a
freshly prepared compound IIIb is very important,
since it tends to disproportionate on handling to give
a mixture of products).
characteristic of amidothiophosphates:
68.47 (Xa)
P
S
P
S
P
O
O
O
O
Me2N
R2N
CH3CN
acacRh(CO)2
IIIb + Xa, Xb
OC
HNR2
O
O
Rh
P
O
P
O
P
P
O
CO
O
O
O
Et2N
Et2N
acac
Rh
Et2N
NEt2
acac
XIa, XIb
XII
S
VIIIa, VIIIb
As a result, an oily substance readily soluble in
methylene chloride and dioxane separated from the
solution. The 31P NMR spectra of compounds XIa,
XIb contained signals of two types of phosphorus
(50 C, 1 mm) contained signals of amines liberated
during their synthesis and also of solvents, including
methylene chloride.
Hence, we established that 2,7-dihydroxynaphtha-
lene behaves quite differently from resorcinol in the
synthesis of arylene amidophosphacyclanes. Stable
tris(arylene phosphacyclanes) can be prepared either
with mixed phosphorus or with (R2N)P=S functions.
centers at
68.18 and 140.85 (XIa) and 66.88 and
140.87 ppmP(XIb). The integral intensity ratios were
1:2. The products obtained after sulfurization and
isolated by column chromatography were fully iden-
tical to compounds VIIIa, VIIIb.
To provide further evidence for the formation of
compounds XIa, XIb, we brought the latter com-
pound into complex fomation with AcacRh(CO)2.
Complex XII was isolated by reprecipitation and
looked as a dark brown powder after drying. Its 31P
NMR spectrum contained a doublet at P 134.07 ppm,
characteristic of phosphamides coordinated with Rh,
EXPERIMENTAL
The IR spectra were measured on a Specord IR-75
instrument in NaCl cells in methylene chloride. The
1H NMR spectra were measured in CDCl3 on a
Bruker H-250 (250 MHz) spectrometer against TMS.
The 31P NMR spectra were obtained on a Bruker
WP-80SY spectrometer (32.4 MHz) against 85%
phosphoric acid.
and a singlet at
68.63 ppm, characteristic of thio-
P
phosphate phosphorus. The integral intensity ratio of
these two signals was 2:1.
Column chromatography was performed on Silica
gel L 100/250. Thin-layer chromatography was
performed on Silufol plates, elution with benzene
dioxane, 3:1 (A), benzene dioxane, 5:1 (B), chloro-
form ethanol, 3:1 (C), and chloroform ethanol, 5:1
Compounds VIIIa, VIIIb, having molecular
cavities, tend to form inclusion compounds. This
1
is proved by the fact that the H NMR spectra of
VIIIa, VIIIb subjected to prolonged vacuum drying
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 8 2003

MACROCYCLIC SYSTEMS ON THE BASIS OF PHOSPHORUS ACIDS
1211
1
(D), development in iodine vapor. All operations were
carried out in dry solvents under argon.
0.79 (B). H NMR spectrum, , ppm: 1.17 t (18H,
CH3), 3.5 m (12H, CH2), 7.35 d, 7.63, 7.79 d (18H,
CH, JPH 13.75 Hz). 31P NMR spectrum (CH2Cl2),
,
3
ppm: 67.15 s. Found, %: C 57.32; H 5.49; N 4.78; PP
10.56. C42H48N3O6P3S3. Calculated, %: C 57.34; H
5.5; N 4.76; P 10.52.
2,7-Bis[(7-hydroxy-2-naphthyl)(diethylamino)-
thiophosphoryloxy]naphthalene (V). A mixture of
0.8 g of amide Ib and 0.26 g of diol II in 5 ml of dry
acetonitrile was stirred for 10 min at room tempera-
ture and then an additional diol II (1.3 g in 7 ml of
dry acetonitrile) was added. After 4-h stirring, 0.1 g
of sulfur was added, and the resulting mixture was left
to stand for 1 day, after which it was filtered,
the solvent was removed in a vacuum, and the residue
was chromatographed (eluent benzene dioxane, 7:1).
Compound V was isolated and dried in a vacuum for
2 h (60 C, 1 mm). Yield 0.39 g (32%), oil. Rf 0.60
Bis(7-hydroxy-2-naphthyl) diethylphosphor-
amidite (IXb). To a solution of 0.31 g of compound
Ib in acetonitrile, 0.5 g of diol II was added with
stirring at room temperature. After 4 h, the solvent
was removed in a vacuum, and the residue was
chromatographed on a column of silica gel, eluent
benzene dioxane, 7:1. The product was dried for 2 h
in a vacuum (1 mm) for 50 C. Yield 0.07 g (12%),
(A), 0.51 (B). 1H NMR spectrum, , ppm: 1.19 t (12H, oil, Rf 0.62 (D). H NMR spectrum, , ppm: 1.19 t
1
3
CH3), 3.52 m (8H, CH2), 6.92 br.s (2H, OH), 7.22 d,
7.34 d, 7.52 s, 7.56 s, 7.78 d, 7.81 d (18H, CH). 31P
NMR spectrum, P, ppm: 67.3 s (CH3CN). Found, %:
C 61.00; H 5.36; N 3.72; P 8.23. C38H40N2O6P2S2.
Calculated, %: C 61.11; H 5.40; N 3.75; P 8.29.
(6H, CH3), 3.51 m (4H, CH2, JPH 14.3 Hz), 4.80 br.s
(2H, OH), 7.02 d, 7.07 s, 7.69 d (6H, CH), 7.22 d,
7.51 s, 7.78 d (6H, CH). 31P NMR spectrum (CH3CN),
P, ppm: 140.81 s.
O,O-Bis(7-hydroxy-2-naphthyl) (dialkylamido)-
thiophosphates Xa, Xb. Diol II, 7.5 mmol, was
added at room temperature to 2.5 mmol of hexaalkyl-
phosphorous triamide Ia, Ib. The resulting mixture
was stirred for 3 h, after which 2.5 mmol of sulfur
was added, and stirring was continued for an addi-
tional 3 h. The mixture was then filtered, the solvent
was removed in a vacuum, and the residue was chro-
matographed on a column of a silica gel. Compound
Xa was eluted with benzene dioxane, 7:1, and
compound Xb, with benzene dioxane, 9:1. The
products were dried in a vacuum (1 mm) for 2 h at
60 C.
Cyclic thiophosphates VIIIa, VIIIb. a. To a solu-
tion of 2 mmol of amide Ia, Ib in 7 ml of acetonitrile,
2 mmol of compound V was added with stirring at
room temperature. The resulting mixture left to stand
for a day. An oily precipitate formed and was washed
with acetonitrile, dissolved in 5 ml of methylene
chloride, and treated with 2 mmol of sulfur. After a
day, the reaction mixture was filtered, and the solvent
was removed in a vacuum. The residue was chroma-
tographed on a column of silica gel, eluent benzene
dioxane, 9:1. The eluent was evaporated at reduced
pressure and the residue was dried in a vacuum
(1 mm) for 2 h at 50 C.
O,O-Bis(7-hydroxy-2-naphthyl) (dimethyl-
amido)thiophosphates (Xa). Yield 50%, mp 108
b. A solution of 1 mmol of diol II in 6 ml of aceto-
nitrile was added with stirring at room temperature to
1
109 C, Rf 0.56 (A), 0.41 (B). H NMR spectrum, ,
ppm: 3.02 d (6H, CH3), 6.00 br.s (2H, OH), 7.00 d,
2
mmol
of
amide
Ib.
After
10-min
3
7.63 s (6H, CH3, JPH 12.1 Hz). 31P NMR spectrum
stirring, 1 mmol of thiophosphate Xa, Xb was added.
The reaction mixture was left to stand for a day. A
precipitate formed and was washed with acetonitrile,
dissolved in 5 ml of methylene chloride, and 2 mmol
of sulfur was added. After 10 h, the mixture was
filtered, the solvent was removed in a vacuum, and
the residue was purified as described above.
(CH3CN), P, ppm: 68.47 s.
O,O-Bis(7-hydroxy-2-naphthyl) (diethyl-
amido)thiophosphates (Xa). Yield 62%, mp 112
1
113 C, Rf 0.48 (B), 0.81 (C). H NMR spectrum, ,
ppm: 1.19 t (6H, CH3), 3.53 m (4H, CH2), 7.00 d,
7.05 s, 7.66 d (6H, CH), 7.24 d, 7.51 s, 7.72 d (6H,
CH), 7.4 br.s (2H, OH). 31P NMR spectrum (CH3CN),
P, ppm: 66.88 s. Found, %: C 63.56; H 5.33; N 3.08;
P 6.84. C24H24NO4PS. Calculated, %: C 63.58; H
5.31; N 3.04; P 6.85.
Compound VIIIa. Yield 0.53 g (50%), mp 108
1
109 C, Rf 0.56 (A), 0.41 (B). H NMR spectrum, ,
3
ppm: 3.02 d (6H, CH3, JPH 12.1 Hz), 6.00 br.s (2H,
OH), 7.00 d, 7.03 s, 7.63 d (6H, CH), 7.22 d, 7.48 s,
7.70 d (6H, CH). 31P NMR spectrum (CH2Cl2),
,
Complex XII. To a solution of 0.5 g of compound
XIa in 5 ml of methylene chloride, a solution of
0.15 g of dicarbonylrhodium(I) acetylacetonate in
7 ml of methylene chloride was added with stirring at
room temperature. The reaction mixture was left to
P
ppm: 68.47 s. Found : M 818 (cryoscopy). Calculated:
M 852.
Compound VIIIb. Yield 78%, mp 93 94 C, Rf
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 8 2003

1212
RASADKINA et al.
stand for a day, and the resulting complex was pre-
cipitated with hexane and dried in a vacuum (1 mm)
for 2 h at 60 C. Yield 0.39 g (49%), mp 51 52 C. IR
estestvennykh i gumanitarnykh nauk. Universitety
Rossii Program (grant no. 990986).
1
spectrum, , cm : 1990 (Rh CO), 1510, 1570 (acac
REFERENCES
1
CO). H NMR spectrum, , ppm: 1.13 t (12H, CH3),
1.45 s, 1.96 s (12H, acac CH3), 3.00 d (6H, CH3),
3.63 m (8H, CH2), 5.31 s (2H, acac CH), 7.35 d,
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.
7.44 s, 7.74 d (12H, CH), 7.31 d, 7.57 s, 7.70 d (6H,
3
CH, JPH 11.55 Hz). 31P NMR spectrum (CH2Cl2),
,
P
ppm: 134.08 d (1JPRh 265 Hz), 68.63 s.
ACKNOWLEDGMENTS
2. Nifantyev, E.E., Rasadkina, E.N., Yankovich, I.V.,
Vasyanina, L.K., Belsky, V.K., and Stash, A.I., Hetero-
atom. Chem., 1988, vol. 9, no. 7, pp. 643 649.
The work was financially supported by the Funda-
mental’nye issledovaniya vysshei shkoly v oblasti
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 8 2003