9
02
BLOKHIN et al.
The yields of IV indicate that method b is more
temperature to 0.2 g (1.8 mmol) of hydroquinone in
8 ml of ethyl acetate. After 24 h, the solvent and excess
amide II were distilled off under reduced pressure
(water-jet pump). Bisphosphorylated hydroquinone V
effective than a, presumably due to higher rate of
phosphorylation of hydroquinone. The oxidation of
IV gave macrocyclic bis-amidophosphate VIII
(
Scheme 4) which showed one broadened signal
was identified by TLC: R 0.79 (A); published data [3]:
f
3
1
at δ 2.35 ppm in the P NMR spectrum. After puri-
Rf 0.80 (A). A solution of 0.41 g (1.8 mmol) of com-
pound I in 13 ml of ethyl acetate was added to the
residue, the mixture was stirred for 24 h at room
temperature, and the solvent was distilled off under
reduced pressure. Yield 1.64 g.
P
fication by column chromatography, compound VIII
was isolated as a red–brown oily material which thick-
ened on storage. Its structure was confirmed by mass
spectrometry.
Biological testing of compounds VII and VIII for
revealed their selective antimicrobial activity [12].
5,9-Bis(diethylamino)-2,2-dimethyl-4,6,8,10-tetra-
oxa-5λ ,9λ -diphospha-1,3,7(1,4)-tribenzenacyclo-
decaphane 5,9-disulfide (VII). a. A solution of 0.2 g
5
5
EXPERIMENTAL
(
6.2 mmol) of elemental sulfur in 20 ml of benzene
was added to 2.60 g of crude compound IV prepared
as described above in a, the mixture was kept for 24 h,
the solvent was distilled off under reduced pressure,
and the residue was purified by column chromatog-
raphy using benzene as eluent. The eluate was evap-
orated, and the product was dried under reduced pres-
sure (10 mm, 50°C, 2 h). Black–red viscous oily sub-
Analysis by thin-layer chromatography was per-
formed using Silufol plates and the following eluents:
benzene–dioxane, 3:1 (A); hexane–dioxane, 3:1 (B),
chloroform–ethanol, 5:1 (C); benzene–dioxane, 5:1
(
D); spoys were visualized by treatment with iodine
vapor and calcination. The mass spectra (MALDI)
were recorded on a Bruker Daltonics Autoflex II mass
spectrometer (nitrogen laser, λ = 337 nm; positive ion
stance. Yield 0.92 g (57%). R 0.67 (A), 0.63 (D).
f
1
H NMR spectrum (CDCl ), δ, ppm: 1.13 t (12H,
CH ), 1.61 s (6H, CH ), 3.26 m (8H, CH , J
3
3
1
detection). The P NMR spectra were obtained from
3
=
3
3
2
PH
solutions in ethyl acetate (IV) or benzene (VII, VIII)
1
1.94 Hz), 7.02 d (4H, CH), 7.12 d (4H, CH), 7.26 s
on a Bruker WP-80SY spectrometer (32.4 MHz) using
31
(
4H, CH). P NMR spectrum, δ , ppm: 67.51, 67.97.
P
1
8
5% phosphoric acid as reference. The H NMR spec-
Found, %: C 57.73; H 6.27; P 10.36. Mass spectrum:
trum was measured in chloroform-d on a Bruker AM-
+
m/z 627.70 [M + Na] . C H N O P S . Calculated,
2
9
38
2
4 2 2
4
00 instrument (400 MHz) relative to TMS.
All syntheses were performed under argon.
N,N,N′,N′-Tetraethyl-2,2-dimethyl-4,6,8,10-tetra-
%: C 57.59; H 6.35; P 10.24. M 604.70.
b. A solution of 0.18 g (5.6 mmol) of elemental
sulfur in 15 ml of benzene was added to 1.64 g of
crude compound IV prepared as described above in b,
the mixture was kept for 24 h, the solvent was distilled
off under reduced pressure, and the residue was puri-
fied by column chromatography using benzene as
eluent. The eluate was evaporated, and the product was
dried under reduced pressure (10 mm, 50°C, 2 h).
Black–red viscous oily substance. Yield 0.71 g (67%).
oxa-5,9-diphospha-1,3,7(1,4)-tribenzenacyclodeca-
phane-5,9-diamine (IV). a. Hexaethylphosphorous
triamide (II), 3.35 g (13.5 mmol), was added under
vigorous stirring at room temperature to 1.03 g
(
4.5 mmol) of compound I in 40 ml of ethyl acetate.
After 24 h, the solvent and excess amide II were
distilled off under reduced pressure (water-jet pump).
Bisphosphorylated product III was identified by TLC:
R 0.83 (A), 0.56 (B); published data [5]: R 0.84 (A),
5
,9-Bis(diethylamino)-2,2-dimethyl-4,6,8,10-
f
f
5
5
tetraoxa-5λ ,9λ -diphospha-1,3,7(1,4)-tribenzena-
cyclodecaphane 5,9-dioxide (VIII). Crude compound
IV prepared as described above in b, 1.58 g, was dis-
solved in 20 ml of ethyl acetate, and the mixture was
stirred for 4 h on exposure to air. The originally light
yellow mixture turned red–brown. The solvent was
distilled off under reduced pressure, and the residue
was purified by column chromatography using solvent
system C as eluent. The eluate was evaporated, and the
product was dried under reduced pressure (10 mm,
50°C, 2 h). Yield 0.91 g (51%), red–brown viscous
0
.61 (B). A solution of 0.52 g (4.5 mmol) of hydro-
quinone in 45 ml of ethyl acetate was added to the
crude product, the mixture was stirred for 24 h at room
temperature, and the solvent was distilled off under
reduced pressure. Yield 2.60 g, light brown viscous
3
1
tarry material. R 0.65 (A). P NMR spectrum, δP,
f
ppm: 141.51, 142.08. Mass spectrum, m/z: 542.02
+
+
+
[
M + H] , 563.87 [M + Na] , 579.60 [M + K] .
b. Hexaethylphosphorous triamide (II), 2.0 g
(
7.4 mmol), was added under vigorous stirring at room
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 6 2009