Preparative synthesis of phosphoramidite macroheterorings derived from 2,2-bis(4-hydroxyphenyl)propane and related phenols

Full text of DOI:10.1023/A:1013262120747

Russian Journal of General Chemistry, Vol. 71, No. 8, 2001, pp. 1325 1326. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 8, 2001,
pp. 1403 1404.
Original Russian Text Copyright
2001 by Nifant’ev, Rasadkina, Suvorkin, Gusev.
LETTERS
TO THE EDITOR
Preparative Method of Synthesis
of Phosphoramidite Macroheterorings Derived
from 2,2-Bis(4-hydroxyphenyl)propane and Related Phenols
E. E. Nifant’ev, E. N. Rasadkina, S. V. Suvorkin, and D. V. Gusev
Moscow State Pedagogical University, Moscow, Russia
Received October 17, 2000
Recently we studied first representatives of cyclic
diphosphonites derived from 2,2-bis(4-hydroxy-
phenyl)propane (I) and related hinged dibasic phenols
[1]. Regretfully, these compounds have not found wide
synthetic application, because they can not be modi-
fied by nucleophilic substitution at the phosphorus
atom. In this connection creation of chemically more
active reagents of this class of compounds is an actual
problem.
Bauer et al. [2] recently reported the preparation of
first representatives of cyclic diphosphoramidites on
the basis of 2,2-bis(4-hydroxyphenyl)propane and
rigorously proved their structure. However, this work
has no preparative value.
We showed that the target macroheterocycles II
can be easily formed in high yields by the reaction of
equimolar amounts of hexaalkylphosphorous tri-
amides and bisphenol I at 20 C (Scheme 1).
Scheme 1.
A
A
O
O
O
O
A
A
O
O
O
NR2
S
R2N
S
S
P
P NR2
P
A
P(NR2)3 + HO
OH
R2N P
O
I
IIa, IIb
IIIa, IIIb
CH3
CH3
A
=
R = CH3 (a), C2H5 (b),
.
Phosphorodiamidite II is easily oxidized and reacts
with protic nucleophiles (Scheme 2).
Bis(O,O -isopropylidenedi-p-phenylene) bis-
(dimethylphosphorothioamidate) (IIIa). Yield 58%
(per two stages), mp 118 120 C, Rf 0.86 [benzene
dioxane, 3:1 (A)], 0.86 [hexane dioxane, 3:1 (B)],
Scheme 2.
1
and 0.90 [chloroform methanol, 3:1 (C)]. H NMR
A
O
O
O
O
spectrum (CDCl3), , ppm: 1.62 s, 1.64 s [12H,
P OC6H5
3
IIa + C6H5OH
C6H5O P
C(CH3)2], 2.95 d [12H, N(CH3)2, JPH 11.96 Hz],
A
7.05 s, 7.07 s (4H, CH Ar), 7.15 s, 7.17 s (4H,
CH Ar). 31P NMR spectrum (C6H6), P, ppm: 67.8 s.
Found, %: C 61.10; H 6.12; P 9.13. C34H40N2O4P2S2.
Calculated, %: C 61.24, H 6.05, P 9.29.
IV
We also demonstrated the possibility of synthesis
of analogous systems containing two different arylene
fragments (A and B) (Scheme 3).
Bis(O,O -isopropylidenedi-p-phenylene) bis-
1070-3632/01/7108-1325$25.00 2001 MAIK Nauka/Interperiodica

1326
NIFANT’EV et al.
Scheme 3.
A
B
O
O
O
O
A
O
O
1) HO
2) S
B
OH;
NR2
S
R2N
S
P
P(NR2)2
P
A
OH
(R2N)2P
2P(NR2)3 + HO
Va, Vb
Br
Br
(a),
CH3
CH3
Ph
Ph
=
V,
B
(b).
Br
Br
1
(diethylphosphorothioamidate) (IIIa). Yield (per
two stages) 63%, mp 94 95 C, Rf 0.72 (A), 0.70 (B),
185 193 C, Rf 0.54 (D). H NMR spectrum (CDCl3),
, ppm: 1.12 s (12H, CH2CH3), 1.59 s [12H,
C(CH3)2], 3.22 3.66 m (8H, CH2CH3), 7.18 s, 7.32 s
(12H, CH Ar). 31P NMR spectrum (CHCl3), P, ppm:
68.2 s. [M]+ 1038.48. Found, %: C 44.16; H 4.62; P
5.12. C38H44Br4N4O4P2S2. Calculated, %: C 43.95, H
4.27; P 5.97.
1
and 0.83 (C). H NMR spectrum (CDCl3), , ppm:
3
1.11 t (12H, NCH2CH3, JPH 6.40 Hz), 1.63 s [12H,
C(CH3)2], 3.41 q (8H, NCH2CH3), 7.07 s, (4H, H Ar),
7.15 s, 7.17 s (4H, CH Ar). 31P NMR spectrum
(C6H6), P, ppm: 67.0 br.s. Found, %: C 63.29; H
6.72; P 8.68. C38H48N2O4P2S2. Calculated, %: C
63.14, H 6.69, P 8.57.
1
The H NMR spectra were recorded on a Bruker
WM-250 (250 MHz) spectrometer against TMS. The
proton singals were assigned on the basis of double
resonance data. The 31P {H1} NMR spectra were
recorded on a Bruker WP-80 SY (32.4 MHz) spectro-
meter against external 85% phosphoric acid. Thin-
layer chromatography was performed on Silufol plates.
Bis(O,O -isopropylidenedi-p-phenylene) bis-
(phenyl phosphite) (IV). Yield 67%, mp 119 121 C,
Rf 0.89 (A), 0.74 (B), and 0.94 (C). H NMR spec-
trum (CDCl3), , ppm: 1.64 s [12H, C(CH3)2], 6.98
7.42 m (26H, CH Ar). 31P NMR spectrum (CHCl3),
P, ppm: 128.5 s. Found, %: C 72.09; H 5.45, P 8.82.
C42H38O6P2. Calculated, %: C 71.99, H 5.47, P 8.84.
1
ACKNOWLEDGMENTS
O,O -Isopropylidenedi-p-phenylene O,O -di-
phenylmethylenedi-p-phenylene bis(dimethyl-
phosphorothioamidate) (Va). Yield 52%, mp 163
The work was financially supported by the Uni-
versitety
Rossii fundamental’nye
issledovaniya
1
164 C, Rf 0.31 [CHCl3 CCl4, 1:1 (D)]. H NMR
Program (project no. 2211).
spectrum (CDCl3), , ppm: 1.12 s (12H, CH2CH3),
1.58 s [6H, C(CH3)2], 3.31 q (8H, CH2CH3), 7.01
7.46 m (26H, CH Ar). 31P NMR spectrum, (CHCl3),
P, ppm: 66.6 s. [M]+ 848.4. Found, %: C 67.16; H
6.85; P 7.12. C48H52N2O4P2S2. Calculated, %: C
68.06; H 6.19; P 7.31.
REFERENCES
1. Blokhin, Y.I., Gusev, D.V., Belsky, V.K., Stash, A.I.,
and Nifant’ev, E.E., Phosphorus, Sulfur Silicon, 1995,
vol. 102, pp. 143 154.
O,O -Isopropylidenedi-p-phenylene O,O -iso-
propylidenebis(3,5-dibromo-p-phenylene) bis(di-
ethylphosphorothioamidate) (Vb). Yield 52%, mp
2. Bauer, I., Habicher, W.D., Jones, P.G., Thonnessen, H.,
and Schmutzler, R., Phosphorus, Sulfur Silicon, 1998,
vol. 143, pp. 19 31.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 8 2001