, 2005, 15(2), 53–54
Interaction of 2-diethylamino-5,5-dimethyl-1,3,2-dioxaphosphorinane with
ortho-hydroxyphenols
Edward E. Nifantiev,*a Vera I. Maslennikova,a Tatyana V. Guzeeva,a Wolf D. Habicher,b Ingmar Bauer,b
Konstantin A. Lyssenkoc and Mikhail Yu. Antipinc
a Moscow State Pedagogical University, 119021 Moscow, Russian Federation. Fax: +7 095 248 0162; e-mail: chemdept@mtu-net.ru
b Dresden University of Technology, D-01062 Dresden, Germany.
c A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991 Moscow, Russian Federation.
Fax: +7 095 135 5085; e-mail: kostya@xray.ineos.ac.ru
DOI: 10.1070/MC2005v015n02ABEH002098
The interaction of 2-diethylamido-5,5-dimethyl-1,3,2-dioxaphosphorinane with pyrocatechol, pyrogallol or pyrogallolarene results
in the formation of 1,3-bis(5',5'-dimethyl-1',3',2'-dioxaphosphorinanoxy)-2,2-dimethylpropane; in the case of pyrogallolarene, the
second product is a hemicarceplex whose calixarene cups are linked by two phosphoneopentylene bridges.
1
2-Amino-1,3,2-diheterophosphocyclanes are readily available
and have a high phosphorylating capacity of proton-bearing
nucleophiles due to the rupture of an exocyclic P–N bond. They
are widely used in the design of various organophosphorus
compounds,1 including the phosphorylation of complex polyol
systems. In particular, the phosphorylation of resorcinarenes
using 2-amino-1,3,2-diheterophosphorinanes gave high yields
of individual conformers containing eight specifically oriented
phosphorinane fragments on the periphery of the molecule.2
Here, we consider a formally similar interaction between
2-diethylamino-5,5-dimethyl-1,3,2-dioxaphosphorinane 1 and
pyrogallolarene 2. It is well known that ortho-hydroxyphenols
react with diheterophosphocyclanes in a complex manner;3 there-
fore, phosphorinane 1 was first introduced into reaction with
model compounds 3 (pyrocatechol 3a and pyrogallol 3b). The
reactions were conducted in dioxane at various reagent ratios
and temperatures.
We found that the reaction of model compounds 3 with phos-
phorinane 1 at 18–22 °C and an equimolar reagent ratio results
in the formation of hexacoordinated phosphorus derivatives 4
(Scheme 1).
Reactions proceed rapidly; 10 min after the mixing of reagents,
a signal with dP 148 ppm due to phosphorinane 1 completely
disappeared from the 31P NMR spectra of the reaction mixture,
and two signals with equal integral intensities appeared: a singlet
with dP 121 ppm and a doublet with dP –95 ppm and JPH
820 Hz. The 1H NMR spectra of compounds 4 are in agreement
with the proposed formula.†
The heating of the reaction mixture (50–55 °C, 2 h) or standing
at room temperature for 3 days results in the dismutation of
compounds 4 with the formation of 1,3-bis(5',5'-dimethyl-
1',3',2'-dioxaphosphorinanoxy)-2,2-dimethylpropane 5 and tetra-
coordinated phosphorus derivatives (Scheme 1). The structure
of compound 5 was supported by NMR spectroscopy,‡ and the
structure of its thione derivative 6 was supported by X-ray
powder diffraction analysis.§
The bond lengths and angles in 6 are characterised by the
expected values for this class of compounds (Figure 1).
The conformation of the six-membered rings is a chair with
the P=S bond in the equatorial position and an alkoxy group
in the axial one. The conformation of the P(1)O(3)C(11)C(13)
and P(2)O(6)C(12)C(13) fragments is practically the same with
torsion angles of 175.7° and 169.6°, respectively, while the
mutual arrangement of six-membered rings with respect to the
C(13)C(14)C(15) fragment is principally different, as illustrated
by the pseudotorsion angles S(1)P(1)C(13)C(15) and S(2)P(2)–
C(13)C(15) equal to 46.7° and 163.5°, respectively.
4a: 1H NMR (200 MHz, CDCl3) d: 0.64 (s, 6H, Me), 0.88 (s, 3H,
†
Me), 1.01 (t, 6H, NCH2Me, 3JHH 6.6 Hz), 1.14 (s, 3H, Me), 2.1 (q, 4H,
NCH2Me, 3JHH 6.6 Hz), 3.2 (dd, 2H, OCH2e , 2JHH 10.4 Hz, 3JPH 11.0 Hz),
3.35 (d, 2H, OCH2, 3JPH 9.9 Hz), 3.48 (d, 2H, OCH2, 3JPH 6.0 Hz), 4.05
(d, 2H, OCH2a , 2JHH 10.4 Hz), 6.42 (d, 1H, PH, 1JPH 820 Hz), 6.48–6.95
(10H, Harom., H2N).
OH
OH
O
O
O
5: 1H NMR (200 MHz, CDCl3) d: 0.72 (s, 6H, Me), 0.97 (s, 6H, Me),
O
‡
X
OH
X
O P
Et2N
P
1.24 (s, 6H, Me), 3.29 (dd, 4H, OCH2e , JHH 10.4 Hz, JPH 10.4 Hz),
2
3
1
a
3
3
3.57 (d, 4H, OCH2, JPH 6.0 Hz), 4.13 (d, 4H, OCH2 , JHH 10.4 Hz).
– HNEt2
31P NMR (32.4 MHz, CDCl3) d: 121.
3a X = H
3b X = OH
§
Crystallographic data for 6: crystals of C15H30O6P2S2, M = 432.45, are
triclinic, space group P1, at 120 K: a = 8.214(2), b = 12.648(3) and c =
= 12.880(3) Å, a = 62.290(4)°, b = 85.762(5)°, g = 73.147(5)°, V =
1130.8(5) Å3, Z = 2 (Z' = 1), dcalc = 1.270 g cm–3, m(MoKα) = 4.02 cm–1,
F(000) = 460. Intensities of 8155 reflections were measured with a
Smart CCD diffractometer [l(MoKα) = 0.71072 Å, w-scans, 2q < 52°],
and 4350 independent reflections [Rint = 0.0478] were used in the further
refinement. The structure was solved by the direct method and refined by
the full-matrix least-squares technique against F2 in the anisotropic–
isotropic approximation. Hydrogen atoms were located from the Fourier
synthesis and refined in the isotropic approximation. The refinement
converged to wR2 = 0.1705 and GOF = 1.081 for all independent reflec-
tions [R1 = 0.0710 was calculated against F for 2747 observed reflections
with I > 2s(I)] for 6. All calculations were performed using SHELXTL
PLUS 5.0.
Atomic coordinates, bond lengths, bond angles and thermal param-
eters have been deposited at the Cambridge Crystallographic Data Centre
conts/retrieving.html (or from the CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: +44 1223 336 033; or deposit@ccdc.cam.ac.uk).
Any request to the CCDC for data should quote the full literature citation
and CCDC reference number 266637. For details, see ‘Notice to Authors’,
Mendeleev Commun., Issue 1, 2005.
O
O
P
O
O
P
O
O
3, HNEt2
X
1
– HNEt2
+
X
X
H2NEt2
H
O
O
P –
O
O
O
O
O
O
P
O
4
P
O
P
O
O
O
O
+ phosphates
mix
4a X = H
4b X = OH
5
Scheme 1
Mendeleev Commun. 2005 53
Nifantiev, Edward E.
