196
RASADKINA et al.
Compound XIIIa or XIIIb, 0.04 mmol, was treated
with a solution of 0.2 mmol of dihydric phenol X XII
in 1 ml of acetonitrile, methylene chloride, dioxane,
or ether. After the dismutation of XVb or XVIb was
complete, the solvent was removed, the residue was
dissolved in 2 ml of methylene chloride, 0.5 mmol of
sulfur was added, and the mixture was kept for 40 h
at room temperature. After that the reaction mixture
was filtered, the solvent was distilled off, and the
residue was chromatographed on a column. Cyclic
phosphoramidothioates XXIb and XXIIb were eluted
with 1:2 benzene dioxane. The products were dried
in a vacuum (1 mm Hg, 70 C) for 2 h.
126.9 s (2C, C7,7 H), 134.9 s (2C, C10,10 ), 150.9 d (2C,
C
1,1 O, 2JPC 7.5 Hz), 151.3 d (2C, C3,3 O, 2JPC 8.8 Hz).
135.5 ppm (C6H6). Found, %: C 64.97; H 6.21; N
5P.76. C30H32N2O4P2 0.25C5H11N. Calculated, %:
C 65.93; H 5.90; N 5.13.
Cyclobis(2,6-naphthylene phosphoropiperididi-
te) XLIb. Yield 28%, mp 106 108 C, Rf 0.86 (B). 1H
NMR spectrum, , ppm: 1.5 br.d (12H, CH2),
3
3.29 br.m (8H, CH2N, JPH 6.6 Hz), 7.25 d (4H,
3
C3,7H, JHH 8.8 Hz), 4.45 s (4H, C1,5H), 7.66 d (4H,
3
C4,8H, JHH 8.8 Hz). P 136.6 ppm (C6H6). Found, %:
C 65.87; H 5.92; N 5.15. C30H32N2O4P. Calculated,
%: C 65.93; H 5.90; N 5.13.
Cyclobis(O,O -1,4-phenylene phosphoropiper-
Cyclobis(2,6-naphthylene phosphoromorpho-
ididothioate) XXIb. Yield 30%, oil. Rf 0.89 (B),
1
P
lidite) XLId. Yield 20%, oil. H NMR spectrum, ,
66.6 ppm (CH2Cl2).
3
ppm: 3.36 br.m (8H, CH2N, JPH 5.5, 6.0 Hz), 3.65
Cyclobis(O,O -4,4 -biphenylene phosphoropi-
perididothioate) XXIIb. Yield 35%, mp 118 120 C,
br.d (8H, CH2O), 7.24 d (4H, C3,7H), 4.45 s (4H,
C1,5H), 7.68 d (4H, C4,8H). P 135.2 ppm (CH2Cl2).
1
Rf 0.89 (B). H NMR spectrum, , ppm: 1.64 br.t
3
ACKNOWLEDGMENTS
(12H, CH2), 3.49 m (8H, CH2, JPH 9.2 Hz), 7.32 d
3
3
(8H, CH, JHH 7.6 Hz), 7.54 d (8H, CH, JPH 8.5 Hz),
The study was financially supported by the Univer-
sities of Russia program (project no. UR 05.01.026)
and by the grant of the President of the Russian
Federation for support of leading scientific schools
(project no. NSh-560.2003.3).
66.8 ppm (1,4-dioxane).
P
Dismutation of bisphosphorylated dihydroxy-
naphthalenes XXXI XXXVI. Compound XIIIa
XIIId, 0.4 mmol, was treated with a solution of
0.2 mmol of dihydroxynaphthalene XXV XXX in
1 ml of acetonitrile, methylene chloride, dioxane,
benzene, or diethyl ether. When performing the reac-
tions in acetonitrile, cyclic phosphoramidites
XXXVI XLI separated out as oils, which were
washed with acetonitrile and dried in a vacuum (1 mm
Hg, 70 C) for 2 h.
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3
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7
8
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3
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3
3 4
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3
8.17 d (2H, C4H, JH H 8.8 Hz), 8.21 d (2H, C8H,
3
4
3
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8
JH H 9.9 Hz),
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P
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3
3.19 br.t (8H, CH2N, JPH 8.2, 7.7 Hz); 7.05 s (2H,
C2H), 7.21 br.m (4H, C6,7H), 7.37 d (2H, C4H),
7.62 d (2H, C5H), 8.10 d (2H, C8H). 13C NMR spec-
trum, C, ppm: 24.7 s (2C, CH2), 26.5 s (4C, CH2),
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2
44.5 d (4C, CH2, JPC 23.1 Hz), 108.9 m (2C, C2,2 H),
11. Nifant’ev, E.E., Rasadkina, E.N., Yankovich, I.V.,
Vasyanina, L.K., Bel’skii, V.K., and Stash, A.I.,
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110.2 d (2C, C4,4 H), 120.2 s (2C, C9,9 ), 122.4 s (2C,
C5,5 H), 124.0 s (2C, C6,6 H), 126.8 s (2C, C8,8 H),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 2 2006