Formation of the cage-like phosphoranes with the P-C and P-N bonds in the reactions of 2-(2-benzylidenamino)phenoxy-4-tert-butylbenzo-1,3,2-dioxaphosphol with ethyl mesoxalate and ethyl trifluoropyruvate

Article abstract of DOI:10.1007/s11172-013-0147-5

The reaction of 2-(2-benzylidenamino)phenoxy-4-tert-butylbenzo-1,3,2- dioxaphosphol with ethyl mesoxalate and ethyl trifluoropyruvate resulted in the formation of tricyclic phosphoranes with the P-C and P-N bonds. The adduct emerged from the initial react

Full text of DOI:10.1007/s11172-013-0147-5

Russian Chemical Bulletin, International Edition, Vol. 62, No. 4, pp. 1091—1096, April, 2013
1091
Formation of the cageꢀlike phosphoranes with the P—C and P—N bonds
in the reactions of 2ꢀ(2ꢀbenzylidenamino)phenoxyꢀ4ꢀtertꢀbutylbenzoꢀ1,3,2ꢀ
dioxaphosphol with ethyl mesoxalate and ethyl trifluoropyruvate*
M. N. Dimukhametov, V. F. Mironov, D. B. Krivolapov, E. V. Mironova, and R. Z. Musin
A. E. Arbuzov Institute of Organic and Physical Chemistry Kazan Scientific Center of the Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843) 273 2253. Eꢀmail: mironov@iopc.ru
The reaction of 2ꢀ(2ꢀbenzylidenamino)phenoxyꢀ4ꢀtertꢀbutylbenzoꢀ1,3,2ꢀdioxaphosphol with
ethyl mesoxalate and ethyl trifluoropyruvate resulted in the formation of tricyclic phosphoranes
with the P—C and P—N bonds. The adduct emerged from the initial reaction of the PIII
derivative with the activated ketone (1 : 1), further underwent the transformation via the intraꢀ
molecular reaction involving the benzylideniminoaryl substituent, which resulted in the formaꢀ
tion of the cageꢀlike phosphoranes.
Key words: organic derivatives of hypercoordinated phosphorus(V), oxidative addition of
P
III derivatives to heteroatomic multiple bonds, cageꢀlike phosphoranes, trigonal bipyramidalꢀ
type structures, stereoselectivity, Xꢀray crystallography.
Development of new methods for the synthesis of hyꢀ
percoordinated phosphorus derivatives, key intermediates
in phosphorylation and dephosphorylation reactions proꢀ
ceeding in living cells, is an actual direction in the chemꢀ
istry of organoelement compounds.1,2 The PV derivatives
are intermediates in many important reactions in organic
chemistry of phosphorus, such as nucleophilic substituꢀ
tion at PIV atom, Wittig, Mitsunobu, Evans and other
reactions; they are used in organic synthesis for the formaꢀ
tion of C—C (oxaphosphorane condensation), C—X
(X = O, N, S) and other bonds.3,4 Synthesis of phosphoꢀ
ranes includes the oxidative addition reactions of PIII deꢀ
rivatives to various organic and inorganic agents, to comꢀ
pounds containing heteroatomic multiple bonds, different
rearrangements, etc.5,6
In the last years, we are working on the development of
a new approach to the synthesis of derivatives of hyperꢀ
coordinated phosphorus, which is based on the cascade
reactions of PIII derivatives containing a carbonyl group in
one of the substituents, which are initiated by activated
carbonyl compounds, such as chloral, hexafluoroacetone,
etc.7 In development of this approach, in the present work we
for the first time used in the synthesis of cageꢀlike phosꢀ
phoranes a PIII derivative, viz., 2ꢀ(2ꢀbenzylidenaminoꢀ
phenoxy)ꢀ5ꢀtertꢀbutylbenzoꢀ1,3,2ꢀdioxaphosphol (1)
containing a C=N bond in one of the substituents, ethyl
esters of mesoxalic and trifluoropyruvic acid (2a,b) were
used as the carbonyl compounds initiating the casꢀ
cade process.
The reaction of the indicated compounds proceeded
under mild conditions and quantitatively led to the formaꢀ
tion of stereoisomeric compounds 3. The process apparꢀ
ently included a nucleophilic attack by the phosphorus
atom on the carbonyl carbon atom and the initial formaꢀ
tion of the bipolar ion A, the further stabilization of which
proceeded through the intramolecular attack of the C=N
bond by the alkoxide anion and finalized by the formation
of the P—N bond (Scheme 1). The tertꢀbutyl group in the
phenylene fragment plays the role of an anchor, firmly
differentiating the axial and the equatorial positions of the
oxygen atoms of the benzophosphol fragment in the phosꢀ
phorus trigonal bipyramid, thus simplifying interpretation
of NMR data.
Based on the 13C and 31P NMR spectra, the comꢀ
pounds obtained were identified as spirophosphoranes 3a,b
with the phosphorus—carbon and phosphorus—nitrogen
bonds. Their structure was also confirmed by electron imꢀ
pact mass spectrometry: the mass spectra contained the
molecular ion peaks [M]+• with m/z 565 (3a) and 561 (3b).
The general fragmentation process of these molecules upon
electron impact is the formation of ions [M – Me]+ (550
and 546, respectively) and ions [M – COOEt] (492 and
488, respectively).
It should be noted that compound 3a contains two
chiral centers (P(1) and C(6)) and is formed as a mixture
of two diastereomers (d1, d2) of the composition of 3 : 2.
In the 13Cꢀ{1H} NMR spectrum, carbon atoms C(8) and
* Dedicated to academician of the Russian Academy of Sciences
I. P. Beletskaya on the occasion of her anniversary.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 1090—1095, April, 2013.
1066ꢀ5285/13/6204ꢀ1091 © 2013 Springer Science+Business Media, Inc.

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Dimukhametov et al.
Scheme 1
P(1)—N(5) bond, which can be probably explained by two
reasons. First, this is a compromise reached for the
arrangement of two highly apicophilic fiveꢀmembered
heterocycles annulated with respect to this bond: in such
an arrangement each of them has the axialꢀequatorial
orientation. The second reason seems more important,
this is the competition for the second axial place of the
P—O bond of the tertꢀbutylbenzodioxaphosphol ring
P(1)O(1)C(9)C(14)O(3), which has the flattened envelop
conformation (the fragment O(1)C(9)C(14)O(3) is plaꢀ
nar within 0.002(3) Å, whereas the P(1) atom deviates
from this plane by 0.1224(6) Å). The base of the trigonal
bipyramid O(2)P(1)O(3)C(8) is almost ideally planar
(within 0.0023(6)); the axial atoms O(1) and N(5) deviate
from it by –1.700(2) and 1.732(2) Å, respectively. The
cycle P(1)O(2)C(3)C(4)N(5) also has the flattened envelꢀ
op conformation (the fragment O(2)N(5)C(3)C(4) is plaꢀ
nar within 0.013(2) Å, atom P(1) deviates from the plane
by 0.0633(6) Å). The rigidity of the structure, apparently,
forces the cycle P(1)C(8)O(7)C(6)N(5) to adopt a similar
conformation (the fragment C(8)O(7)C(6)N(5) is planar
within 0.036(2) Å, atom P(1) deviates by 0.4222(6) Å), in
which the C(29)F3 group and atom O(3) occupy the axial
positions (they deviate by 1.450(3) and –1.944(2) Å),
whereas the C(30)(O)OEt group and atom O(2) are equaꢀ
torial (the deviations of C(30) and O(2) are of –0.993(3)
R1 = R2 = COOEt (a); R1 = COOEt, R2 = CF3 (b)
C(6) resonate as two doublets at C 83.65 and 83.56
C(16)
(1JPC = 145.6 and 144.5 Hz), 88.12 and 88.06 (2JPNC
=
C(18)
C(15)
C(11)
C(17)
= 17.2 Hz), which belong to the two diastereomers. The
signals of the ipsoꢀcarbon atoms C(3), C(4), C(9), C(14),
C(23) are also doubled in pairs. The ethoxy groups in the
ethoxycarbonyl substituents are equivalent in one diasteꢀ
reomer (d2) and considerably differ in the other one (d1),
whereas the carbonyl groups themselves are nonequivaꢀ
lent in both diastereomers. The interpretation of the sigꢀ
nals for the carbon atoms of the dioxaꢀ and oxazapheꢀ
nylene fragments was made with allowance for the splitꢀ
ting of the signals in the 13C NMR spectrum, as well as
based on the differing screening effects of orthoꢀ, metaꢀ,
and paraꢀcarbon atoms by the tertꢀbutyl substituent and
the O and N atoms. Phosphorane 3b with three chiral
centers (P(1), C(6), C(8)) is a mixture of four diaꢀ
stereomers (d1—d4), which are formed in the ratio of
(43 : 37 : 10 : 10). Diastereomers d1 and d2 gradually crysꢀ
tallize, and the structure of one of them (solvate with CCl4
of the composition 1 : 1) was confirmed by Xꢀray diffracꢀ
tion analysis (Fig. 1, Table 1). The configurations of atꢀ
oms C(6), C(8), and P(1)8 in the crystal of the isolated
diastereomer (racemate) are S(R), R(S), and R(S), reꢀ
spectively. The phosphorus atom has a nearly right triꢀ
gonalꢀbipyramidal configuration. The structure has a speꢀ
cific feature of the antiapicophilic arrangement of the
C(12)
C(10)
C(9)
C(13)
O(4)
O(1)
P(1)
C(32)
C(14)
O(3)
C(31)
O(5)
F(1)
O(2)
C(30)
C(8)
C(29)
F(2)
C(3)
O(7)
C(19)
F(3)
C(28)
C(24)
N(5)
C(6)
C(4)
C(27)
C(26)
C(20)
C(23)
C(22)
C(21)
C(25)
Fig. 1. Spatial structure of one of the diastereomers of comꢀ
pound 3b in crystal (the solvent molecule of CCl4 is not shown).

Cage phosphoranes bearing P—C and P—N bonds
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 4, April, 2013
1093
Table 1. Selected bond distances (d), bond () and torsional () angles (deg)
Parameter
Bond
Value
Parameter
Bond angle
Value
Parameter
Bond angle
Value
d/Å
/deg
/deg
P(1)—O(1)
P(1)—O(2)
P(1)—O(3)
P(1)—N(5)
P(1)—C(8)
O(1)—C(9)
O(2)—C(3)
O(3)—C(14)
O(7)—C(8)
O(7)—C(6)
N(5)—C(4)
N(5)—C(6)
C(3)—C(4)
C(9)—C(14)
1.698(2)
1.618(2)
1.623(2)
1.738(2)
1.894(2)
1.378(3)
1.398(3)
1.394(3)
1.401(3)
1.463(3)
1.399(3)
1.431(3)
1.379(3)
1.374(4)
O(1)—P(1)—N(5)
O(1)—P(1)—C(8)
O(2)—P(1)—O(3)
O(2)—P(1)—N(5)
O(2)—P(1)—C(8)
O(3)—P(1)—N(5)
O(3)—P(1)—C(8)
N(5)—P(1)—C(8)
P(1)—O(1)—C(9)
P(1)—O(2)—C(3)
P(1)—O(3)—C(14)
P(1)—C(8)—C(29)
P(1)—C(8)—C(30)
C(6)—O(7)—C(8)
174.6(1)
89.0(1)
113.23(9)
91.3(1)
126.2(1)
92.6(1)
120.5(1)
86.2(1)
111.6(2)
114.1(2)
113.0(2)
110.9(2)
110.4(2)
115.3(2)
111.5(2)
118.1(2)
120.7(2)
O(2)—C(3)—C(4)
N(5)—C(4)—C(3)
O(7)—C(6)—N(5)
P(1)—C(8)—O(7)
112.7(2)
110.2(2)
106.9(2)
108.7(2)
Torsion angle
/deg
O(2)—P(1)—N(5)—C(4)
O(2)—P(1)—C(8)—C(29)
O(2)—P(1)—C(8)—C(30)
N(5)—P(1)—C(8)—C(29)
N(5)—P(1)—C(8)—C(30)
P(1)—O(2)—C(3)—C(4)
C(31)—O(5)—C(30—C(8)
P(1)—N(5)—C(4)—C(3)
P(1)—N(5)—C(6)—C(23)
C(29)—C(8)—C(30—O(5)
–2.4(2)
9.3(2)
133.0(2)
98.2(2)
–138.2(2)
–4.6(3)
179.8(2)
0.2(2)
107.2(2)
179.2(2)
P(1)—N(5)—C(4)
P(1)—N(5)—C(6)
C(4)—N(5)—C(6)
Bond angle
/deg
O(1)—P(1)—O(2)
O(1)—P(1)—O(3)
89.50(9)
92.01(9)
a mixture was stirred for another 1 h and allowed to stand for
16 h. The following day, a precipitate formed was filtered off and
washed with benzene (3 mL). The salt obtained after drying
weighed 1.20 g. The solvent was evaporated from the filtrate, the
residue was kept for 1 h in vacuo (0.1 Torr) to obtain compound 1
3.33 g (96%) as light yellow oil. Found (%): C, 70.43; H, 5.77;
N, 3.61; P, 8.06. C23H22NO3P. Calculated (%): C, 70.59; H, 5.63;
N, 3.58; P, 7.93. 31Pꢀ{1H} NMR (CH2Cl2): P 128.4.
and 0.596(2) Å). In the absence of strong intermolecular
interactions, the crystal packing of compound 3b is stabiꢀ
lized by intraꢀ and intermolecular short contacts of the
...
...
C—H O type: C(28)—H(28) O(3) (d(C—H) 0.95 Å,
...
...
d(H O) 2.46 Å, d(C O) 3.290(4) Å, CHO 146.0) and
...
C(22)—H(22)...O(4) (d(C—H) 0.95 Å, d(H O) 2.55 Å,
...
d(C O) 3.484(3) Å, CHO 170.0, symmetry operation
1 + x, y, z, respectively).
3,4ꢀBenzoꢀ1,1ꢀ(4ꢀtertꢀbutylphenylenedioxy)ꢀ3,3ꢀbis(ethoxyꢀ
carbonyl)ꢀ6ꢀphenylꢀ5ꢀazaꢀ2,7ꢀdioxaꢀ1ꢀphosphabicyclo[3.3.01,5]ꢀ
octane (3a). A solution of compound 2a (1.16 g, 6.67 mmol) in
CCl4 (5 mL) was added dropwise to a solution of 2ꢀ(2ꢀNꢀbenzꢀ
ylidenaminophenoxy)ꢀ5ꢀtertꢀbutylbenzoꢀ1,3,2ꢀdioxaphosphol 1
(2.6 g, 6.65 mmol) in anhydrous CCl4 (40 mL) with stirring
under argon over 30 min. After all the chlorophosphite was addꢀ
ed, the reaction a mixture was stirred for another 1 h and allowed
to stand for 16 h. The following day, the solvent was evaporated
in vacuo (10 Torr) and than was kept for 1 h at 0.1 Torr. The
residue was a light yellow oily liquid, which upon prolong (more
than 1 month) storage under the layer of dry pentane crystalꢀ
lized. The mass of the crystals after drying in vacuo was 3.27 g
(87%), m.p. 130—132 C (from pentane). Found (%): C, 63.89;
H, 5.45; N, 2.31; P, 5.64. C30H32NO8P. Calculated (%): C, 63.72;
H, 5.66; N, 2.48; P, 5.49. MS, m/z (relative intensity (%),
Experimental
NMR spectra were recorded on a Bruker Avanceꢀ400 specꢀ
trometer relative to the signal of the solvent (CDCl3) residual
protons (1H) and the carbon atoms (13C), or relative to the exterꢀ
nal standard H3PO4 (31P). GLCꢀMS spectrometric studies were
carried out on a DFS Thermo Electron Corporation instrument
(Germany) with an Agilent DBꢀ5MS capillary column (length
30 m, diameter 0.254 mm). Ionization by electron impact, the
energy of ionizing electrons was 70 eV, the temperature of the
source of ions was 280 C, helium was the carrier gas. The mass
spectral data were processed using the Xcalibur program. A samꢀ
ple under study before injection into the instrument was diluted
in the chromatographically pure carbon tetrachloride in the conꢀ
centration of ~0.1 wt.% Elemental analysis was performed on
a EuroVectorꢀ3000 analyzer (C, H, N), as well as manually by
pyrolysis of the sample in the flow of oxygen (P).
2ꢀ(2ꢀNꢀBenzylidenaminophenoxy)ꢀ5ꢀtertꢀbutylbenzoꢀ1,3,2ꢀ
dioxaphosphol (1). 5ꢀtertꢀButylꢀ2ꢀchlorobenzoꢀ1,3.2ꢀdioxaphosꢀ
phol (2.05 g, 8.89 mmol) in benzene (10 mL) was added dropꢀ
wise over 10 min to a mixture of 2ꢀNꢀbenzylidenaminophenol
(1.75 g, 8.88 mmol) and triethylamine (1 g, 9.90 mmol) in anhyꢀ
drous benzene (30 mL) with stirring under argon at room temꢀ
perature. After all the chlorophosphite was added, the reaction
+
max.), ion: 565 (80.0) M •, 550 (7.5) [M – CH3]+, 519 (5.9)
[M – C2H6O]+, 492 (17.6) [M – C(O)OC2H5]+, 391 (57.7)
[M – C7H10O5]+, 195 (72.2) [C13H9NO]+, 91 (100.0) [C6H5CH2]+,
77 (13.9) [C6H5]+. 1H NMR (CDCl3), : 0.74, 0.77 (both t,
H(31), H(34), 3JHH = 7.1 Hz); 1.17, 1.18 (both t, H(31), H(34),
3JHH = 7.1 Hz (d1, d2)); 1.29, 1.30 (both s, C(16)—C(18) (d1, d2));
3.73—3.74, 3.86—3.88, 4.23—4.25, 4.30—4.33 (all m, H(30),
3
H(32), ABꢀparts of four ABX3 spectra, JH(A)H(B) = 10.0—12.0
3
3
Hz, JH(A)H(X) = 7.1 Hz, JH(B)H(X) = 7.1 Hz (d1, d2)); 7.75
3
3
(br.m, H(24), JHH = 7.1 Hz (d1, d2)); 7.47 (m, H(25), JHH
= 7.5 Hz, 3JHH = 7.1 Hz (d1, d2)); 7.43 (m, H(26), 3JHH = 7.5 Hz
=

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Dimukhametov et al.
4
4
(d1, d2)); 7.04 (m, H(10), JHH = 2.2 Hz, JPOCCH = 1.2 Hz,
5JHH = 1.1 Hz); 6.98 (m, H(10), 4JHH = 2.2 Hz, 4JPOCCH = 1.2 Hz,
5JHH = 1.2 Hz (d1, d2)); 5.70 (br.s, H(6) (d1, d2)); 6.37, 6.39
cyclo[3.3.01,5]octane 3b was obtained by similar procedure from
2ꢀ(2ꢀNꢀbenzylidenaminophenoxy)ꢀ5ꢀtertꢀbutylbenzoꢀ1,3,2ꢀdiꢀ
oxaphosphol 1 (2.13 g, 5.45 mmol) and compound 2b (0.93 g,
5.45 mmol) as light yellow oily liquid, which crystallized upon
standing under the layer of anhydrous pentane. The weight of the
crystals (a mixture of diastereomers d1, d2 of the composition 1 : 1,
a solvate with CCl4 of the composition 1 : 1) after drying in vacuo
was 2.74 g (70%), m.p. 108—110 C (from CCl4). Found (%): C,
48.85; H, 3.33; N, 2.35; P, 4.71. C28H27NO6F3P•CCl4. Calcuꢀ
lated (%): C, 48.67; H, 3.78; N, 1.96; P, 4.34. MS, m/z (relative
3
(both br.d, H(22) (d1, d2)); 7.01 (br.d, H(13), JHH = 8.4 Hz);
6.91 (dm, H(13), 3JHH = 8.4 Hz, 4JPOCCH = 1.2 Hz, 5JHH = 1.1 Hz
(d1, d2)); 6.83, 6.93 (both br.d, H(19), JHH = 7.0—8.0 Hz
(d1, d2)); 6.79 (br.m, H(20) (d1, d2)); 6.83 (br.m, H(21) (d1, d2));
6.81 (br.m, H(12), JHH = 8.3 Hz (d1, d2)). 13C NMR (CDCl3,
3
3
1
150.9 MHz),  : 108.05 (ddd (d), C(22), JHC = 160.2 Hz,
C
3JPNCC = 11.0 Hz, 3JHC(20)CC(22) = 7.8 Hz (d1)); 109.08 (ddd (d),
1
3
3
C(22), JHC = 160.2 Hz, JPNCC = 14.7 Hz, JHC(20)CC(22)
=
intensity (%) max.), ion (the peaks of ions containing the most
1
often encountered isotopes are reported): 561 (100.0) [M]+
,
•
= 7.7 Hz (d2)); 109.92 (br.ddm (br.d), C(10), JHC = 164.0 Hz,
3JPOCC = 8.9 Hz, JH(12)CC(10) = 6.5—7.0 Hz (d1, d2)); 110.70
546(69.3) [M – CH3]+, 488 (14.3) [M – C(O)OC2H5]+,
391(57.7) [M – C5H5O3F3]+, 195(93.5) [C13H9NO]+, 77(23.3)
[C6H5]+. 1H NMR of the mixture of diastereomers d1—d4, :
3
(dd (d), C(13), 1JHC = 164.1 Hz, 3JPOCC = 15.0 Hz (d1)); 109.61
(dd (d), C(13), 1JHC = 163.9 Hz, 3JPOCC = 10.6 Hz (d2)); 111.58
1
3
3
3
(dddm (d), C(19), JHC = 165.0 Hz, JPOCC = 13.2 Hz,
3JHC(21)CC(19) = 9.4 Hz (d1 + d2)); 111.58 (dddm (d), C(19),
0.83 (t, H(32), JHH = 7.1 Hz); 0.84 (t, H(32), JHH = 7.1 Hz
(d1, d2)); 1.10 (t, H(32), 3JHH = 7.1 Hz); 1.11 (t, H(32), 3JHH
=
1JHC = 165.0 Hz, JPOCC = 13.2 Hz, JHC(21)CC(19) = 9.4 Hz
= 7.1 Hz (d3, d4)); 1.31 (s, H(16)—H(18)); 1.32 (s, H(16)—H(18)
(d1, d2)); 1.33 (s, H(16)—H(18)); 1.35 (s, H(16)—H(18) (d3,
3
3
(d1 + d2)); 120.44 (dd (d), C(12), 1JHC = 162.0 Hz, 3JHC(10)CC(12)
=
1
7.8 Hz (d1 + d2)); 123.70 (dd (s), C(21), JHC = 161.1 Hz,
d4)); 3.62 (m, H(31), ABꢀpart of the ABX3 spectrum, 3JH(A)H(B)
=
3JHC(19)CC(21) = 7.3 Hz (d1)); 123.64 (dd (s), C(21), 1JHC = 160.9 Hz,
= 10.7 Hz, JH(A)H(X) = 7.1 Hz, JH(B)H(X) = 7.1 Hz); 3.95
(m, H(31), ABꢀpart of the ABX3 spectrum, 3JH(A)H(B) = 10.7 Hz,
3JH(A)H(X) = 7.1 Hz, 3JH(B)H(X) = 7.1 Hz (d1, d2)); 4.17 (m, H(31),
two ABꢀparts of two ABX3 spectra (d3, d4)); 7.81 (m, H(24)
(d1, d2)); 7.73 (m, H(24) (d3, d4)); 7.52 (m, H(25) (d1—d4)); 7.46
(m, H(26) (d1—d4)); 6.03 (d, H(6), 3JPNCH = 4.4—4.5 Hz); 6.02
3
3
3JHC(19)CC(21) = 7.4 Hz (d2)); 117.90 (dd (s), C(20), JHC
=
1
= 159.1 Hz, 3JHC(22)CC(20) = 6.5 Hz (d1)); 119.79 (dd (s), C(20),
1JHC = 157.5 Hz, JHC(22)CC(20) = 5.3 Hz (d2)); 147.22 (br.m
3
(br.s), C(11) (d1)); 144.67 (br.m (br.s), C(11) (d2)); 143.13
(m (d), C(3), 3JPOCC = 1.5 Hz (d2)); 143.12 (m (d), C(3), 3JPOCC
=
3
1.5 Hz (d1)); 140.32 (br.m (br.s), C(14) (d1)); 142.41 (br.m (br.s),
C(14) (d2)); 147.61 (br.m (br.s), C(9) (d1)); 145.57 (br.m (br.s),
C(9) (d2)); 138.33 (br.m (br.s), C(4) (d1, d2)); 133.62 (m (d),
(d, H(6), JPNCH = 4.4—4.5 Hz (d1, d2)); 6.13 (br.d, H(6),
3
3JPNCH = 4.4—4.5 Hz (d3, d4)); 6.22 (v.br.d, H(22), JHH
=
3
= 7.0—8.0 Hz); 6.18 (v.br.d, H(22), JHH = 7.0—8.0 Hz (d3,
d4)); 6.68 (br.d, H(22), 3JHH = 7.0—8.0 Hz); 6.71 (br.d, H(22),
3
3
2
C(23), JPNCC = 18.7 Hz, JHCCC = 7.2 Hz, JHCC = 6.1 Hz
(d1)); 133.55 (m (d), C(23), 3JPNCC = 18.7 Hz, 3JHCCC = 7.2 Hz,
3JHH = 7.0—8.0 Hz (d1, d2)); 7.14 (dd, H(10), JHH = 1.5 Hz,
4
2JHCC = 6.1 Hz (d2)); 164.67 (m (d), C(29), JPCC = 7.7 Hz,
4JPOCCH = 1.5 Hz); 7.12 (dd, H(10), 4JHH = 1.5 Hz, 4JPOCCH
=
2
3JHCOC = 3.7 Hz (d1)); 164.75 (m (d), C(29), JPCC = 7.3 Hz,
= 1.5 Hz (d1, d2)); 7.04 (d, H(13), JHH = 8.3 Hz); 7.03 (d,
H(13), 4JHH = 8.3 Hz (d1, d2)); 7.02 (d, H(13), 4JHH = 8.3 Hz);
7.01 (d, H(13), 4JHH = 8.3 Hz (d3, d4)); 7.10 (dd, H(19), 3JHH
2
4
3JHCOC = 3.7 Hz (d2)); 164.55 (m (br.d), C(32), 2JPCC = 2.6 Hz,
3JHCOC = 3.6 Hz (d1)); 164.48 (m (br.d), C(32), 2JPCC = 2.5 Hz,
=
3JHCOC = 3.6 Hz (d2)); 88.12 (ddt (d), C(6), JHC = 158.6 Hz,
= 7.8 Hz, JPOCCH = 1.8 Hz); 7.09 (dd, H(19), JHH = 7.8 Hz,
4JPOCCH = 1.6 Hz (d1, d2)); 6.92—6.95 (m, H(20), H(12), H(21)
1
4
3
3JPNCC = 17.2 Hz, 3JHCCC = 4.8 Hz (d1)); 88.06 (ddt (d), C(6),
1JHC = 158.6 Hz, JPNCC = 17.2 Hz, JHCCC = 4.8 Hz (d2));
(d1, d2)). 13C NMR of the mixture of diastereomers d1—d4, 
3
3
C
83.65 (d (d), C(8), 1JPC = 145.6 Hz (d2)); 83.56 (d (d), C(8), 1JPC
(here and further, the splitting of the signal in the 13Cꢀ{1H})
NMR spectrum is given in parentheses: 108.36 (ddd (d), C(22),
= 144.5 Hz (d1)); 62.74 (tq (s), C(30), 1JHC = 148.7 Hz, 2JHCC
=
=
1
2
3
3
= 4.5 Hz (d1)); 62.68 (tq (s), C(30), JHC = 148.7 Hz, JHCC
4.5 Hz (d1)); 62.87 (tq (s), C(30), 1JHC = 149.1 Hz, 2JHCC = 4.5 Hz
(d2)); 164.67 (m (d), C(29), JPCC = 7.7 Hz, JHCOC = 3.7 Hz
(d1)); 164.55 (m (br.d), C(29), 2JPCC = 2.6 Hz, 3JHCOC = 3.6 Hz
(d1)); 164.75 (m (d), C(29), JPCC = 7.3 Hz, JPCOC = 3.7 Hz
(d2)); 164.48 (m (br.d), C(29), 2JPCC = 2.5 Hz, 3JPCOC = 3.6 Hz
(d2)); 34.78 (m (s), C(15), 3JHC(10)CC(15) = 3.7 Hz, 3JHC(12)CC(15)
= 3.7 Hz, JHCCC = 3.7 Hz (d1)); 34.64 (m (s), C(15),
3JHC(10)CC(15) = 3.7 Hz, 3JHC(12)CC(15) = 3.7 Hz, 3JHCCC = 3.7 Hz
(d2)); 31.58 (q.sept (s), C(16)—C(18), 1JHC = 125.7 Hz, 3JHCCC
1JHC = 160.8 Hz, JPNCC = 11.5 Hz, JHC(20)CC(22) = 7.5 Hz);
1
3
109.21 (dddd (d), C(22), JHC = 160.7 Hz, JPNCC = 15.7 Hz,
3JHC(20)CC(22) = 8.1 Hz, JHC(21)C(22) = 1.2 Hz (d1, d2)); 108.72
(ddm (d), C(22), JHC = 160.8 Hz, JPNCC = 12.3 Hz); 109.16
(ddm (d), C(22), 1JHC = 160.7 Hz, JPNCC = 14.1 Hz (d3, d4));
110.90 (ddd (d), C(13), JHC = 164.5 Hz, JPOCC = 15.5 Hz,
3JH(12)CC(13) = 1.0 Hz); 110.01 (ddd (d), C(13), JHC = 164.8
Hz, JPOCC = 11.3 Hz, JH(12)CC(13) = 1.1 Hz (d1, d2)); 110.82
(br.dd (d), C(13), JHC = 165.0 Hz, JPOCC = 14.0 Hz); 110.51
(br.dd (d), C(13), 1JHC = 164.7 Hz, 3JPOCC = 16.3 Hz (d3, d4));
2
3
2
1
3
2
3
3
1
3
1
=
3
3
3
1
3
=
1
1
3
= 4.9 Hz); 31.52 (q.sept (s), C(16)—C(18), JHC = 125.7 Hz,
111.15 (br.ddd (d), C(10), JHC = 161.7 Hz, JPOCC = 9.2 Hz,
3JHCCC = 4.9 Hz (d1 + d2)); 13.17 (qt (s), C(31), C(34), 1JHC
= 127.4 Hz, 3JHCCC = 2.5 Hz (d2)); 13.96 (qt (s), C(31), 1JHC
=
=
=
3JHC(12)CC(10) = 8.3 Hz); 111.20 (br.ddd (d), C(10), JHC
=
1
= 161.6 Hz, 3JPOCC = 9.4 Hz, 3JHC(12)CC(10) = 8.3 Hz (d1, d2));
= 127.7 Hz, 3JHCCC = 2.5 Hz (d1)); 13.98 (qt (s), C(34), 1JHC
111.37 (d, C(10), 3JPOCC = 9.4 Hz); 111.31 (d, C(10), 3JPOCC
=
3
1
= 127.7 Hz, JHCCC = 2.5 Hz (d1)); 127.79 (br.dm (s), C(24),
= 9.4 Hz (d3, d4)); 112.13 (dddd (d), C(19), JHC = 166.0 Hz,
1JHC = 159.7 Hz (d1, d2)); 128.86 (C(25), JHC = 160.3 Hz,
3JPOCC = 13.0 Hz, 3JHC(21)CC(19) = 8.4 Hz, 2JHC(20)C(19) = 1.3 Hz
1
3JHCCC = 7.5 Hz (d1, d2)); 129.78 (dt (s), C(26), 1JHC = 160.4 Hz,
3JHCCC = 7.5 Hz (d1, d2)). 31Pꢀ{1H} NMR (161.9 MHz, CDCl3),
(d1 + d2)); 111.85 (ddm (d), C(19), JHC = 162.0 Hz, 3JPOCC
=
1
3
= 13.5 Hz, JHC(21)CC(19) = 8.3 Hz); 111.86 (ddm (d), C(19),
1JHC = 162.0 Hz, 3JPOCC = 13.5 Hz, 3JHC(21)CC(19) = 8.3 Hz (d3,
d4)); 121.41 (br.dd (d), C(12), JHC = 165.5—166.0 Hz,
3JHC(10)CC(12) = 8.1—8.3 Hz, 4JPOCCC = 1.3 Hz (d1 + d2)); 120.86
 : –8.2 (s, d1, 60%); –7.9 (s, d2, 40%).
3,4ꢀBenzoꢀ1,1ꢀ(4ꢀtertꢀbutylphenylenedioxy)ꢀ3ꢀethoxycarboꢀ
nylꢀ6ꢀphenylꢀ3ꢀtrifluoromethylꢀ5ꢀazaꢀ2,7ꢀdioxaꢀ1ꢀphosphabiꢀ
P
1

Cage phosphoranes bearing P—C and P—N bonds
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 4, April, 2013
1095
1
3
1
(br.dd (d), C(12), JHC = 161.0 Hz, JHC(10)CC(12) = 7.5 Hz,
= 160.4 Hz (d3, d4)); 129.02 (C(25), C(27)), JHC = 160.4 Hz,
4JPOCCC = 1.3 Hz); 120.81 (br.dd (d), C(12), JHC = 161.0 Hz,
3JHCCC = 7.3 Hz); 129.03 (C(25), C(27), JHC = 160.4 Hz,
3JHCCC = 7.3 Hz (d3, d4)); 128.94 (dd (s), C(25), C(27), 1JHC
1
1
3JHC(10)CC(12) = 7.5 Hz, JPOCCC = 1.4 Hz (d3, d4)); 124.20
=
4
(dd (s), C(21), 1JHC = 161.2 Hz, 3JHC(19)CC(21) = 7.7 Hz); 124.17
(dd (s), C(21), 1JHC = 161.2 Hz, 3JHC(19)CC(21) = 7.8 Hz (d1, d2));
123.67 (dd (s), C(21), 1JHC = 161.0 Hz, 3JHC(19)CC(21) = 7.7 Hz);
= 160.3 Hz, JHCCC = 7.4 Hz); 128.92 (dd (s), C(25), C(27),
3
1JHC = 160.3 Hz, JHCCC = 7.4 Hz (d1, d2)); 127.79 (dt (s),
3
C(26), 1JHC = 160.6 Hz, 3JHCCC = 7.6 Hz); 127.77 (dt (s), C(26),
123.64 (dd (s), C(21), JHC = 161.0 Hz, 3JHC(19)CC(21) = 7.6 Hz
1JHC = 160.6 Hz, JHCCC = 7.6 Hz (d1, d2)); 130.17 (dt (s),
1
3
(d3, d4)); 120.41 (dd (s), C(20), 1JHC = 158.8 Hz, 3JHC(22)CC(20)
=
=
C(26), 1JHC = 160.7 Hz, 3JHCCC = 7.6 Hz); 130.15 (dt (s), C(26),
= 7.2 Hz); 117.73 (dd (s), C(20), 1JHC = 159.6 Hz, 3JHC(22)CC(20)
1JHC = 160.7 Hz, JHCCC = 7.6 Hz (d3, d4)). 31Pꢀ{1H} NMR of
3
1
3
= 7.1 Hz (d1, d2)); 120.19 (dd (s), C(20), JHC = 160.8 Hz,
3JHC(22)CC(20) = 8.2 Hz); 118.57 (dd (s), C(20), 1JHC = 164.0 Hz,
3JHC(22)CC(20) = 7.4 Hz (d3, d4)); 148.0 (d.decet (s), C(11),
3JHC(13)CC(11) = 7.3 Hz, 3JHCCC = 3.6—3.8 Hz); 145.14 (d.decet
(s), C(11), JHC(13)CC(11) = 7.3 Hz, JHCCC = 3.6—3.8 Hz (d1,
d2)); 148.66 (m (s), C(11)); 148.67 (m (s), C(11) (d3, d4)); 147.37
the mixture of diastereomers d1—d4,  : –5.8 (q, d1, JFCCP
= 5.1 Hz); –6.3 (q, d2, JFCCP = 5.1 Hz, 80%); –7.4 (br.m, d3,
=
P
3
d4, 20%).
Xꢀray diffraction analysis of a single crystal of compound 3b
was carried out on a Bruker Smart APEX II CCD automatic
diffractometer: graphite monochromator; (MoꢀK) = 0.71073 Å;
ꢀscan technique; temperature of 150 К. Absorption was alꢀ
lowed for semiempirically using the SADABS program.9 The
structure was solved by direct method using the SIR program10
and refined first in isotropic and then in anisotropic approximaꢀ
tion using the SHELXLꢀ97 program.11 Hydrogen atoms in the
structure of 3b were placed in the geometrically calculated posiꢀ
tions and included into refinement using a riding model. All the
calculations were performed using the WinGX12 and APEX213
programs. All the figures and analysis of the intermolecular inꢀ
3
3
3
2
(dd (s), C(9), JHC(13)CC(9) = 6.5 Hz, JHC(10)C(9) = 4.1 Hz);
145.24 (dd (s), C(9), 3JHC(13)CC(9) = 6.9 Hz, 2JHC(10)C(9) = 3.4 Hz
(d1, d2)); 142.88 (m (s), C(3), 3JHCCC = 8.3 Hz, 3JHCCC = 7.6 Hz,
2JHC(19)C(3) = 4.0 Hz, JHC(21)CCC(3) = 1.1 Hz (d1, d2)); 142.0
4
(m (d), C(14), 3JHC(12)CC(14) = 10.7 Hz, 3JHC(10)CC(14) = 7.0 Hz,
2JPOC = 3.8 Hz, JHC(13)C(14) = 2.4 Hz); 139.88 (m (d), C(14),
2
3JHC(12)CC(14) = 8.0 Hz, 3JHC(10)CC(14) = 4.6 Hz, 2JPOC = 4.0 Hz,
2JHC(13)C(14) = 1.4 Hz (d1, d2)); 139.27 (m (d), C(4), JHCCC
=
=
3
3
2
2
= 7.5 Hz, JHCCC = 7.5 Hz, JPNC = 2.7 Hz, JHC(22)C(4)
= 2.2 Hz); 139.25 (m (d), C(4), 3JHCCC = 7.5 Hz, 3JHCCC = 7.5 Hz,
2JPNC = 2.7 Hz, JHC(22)C(4) = 2.2 Hz (d1, d2)); 134.68 (m (d),
2
C(23), 3JPNCC = 18.5 Hz, 3JHCCC = 6.0—7.0 Hz); 134.61 (m (d),
C(23), 3JPNCC = 18.5 Hz, 3JHCCC = 6.0—7.0 Hz (d1, d2)); 133.68
Table 2. Parameters of the crystal of compound 3b and condiꢀ
tions of Xꢀray diffraction experiment
(m (d), C(23), 3JPNCC = 18.4 Hz); 133.61 (m (d), C(23), 3JPNCC
=
1
= 18.2 Hz (d3, d4)); 123.17 (qd (qd), C(29), JFC = 287.6 Hz,
2JPCC = 8.4 Hz (d1 + d2)); 90.32 (ddt (d), C(6), 1JHC = 161.2 Hz,
Parameter
Value
3JPNCC = 19.5 Hz, JHCCC = 5.0 Hz); 90.27 (ddt (d), C(6),
3
Color
Gabitus
Molecular formula
Molecular weight
Colorless
Prismꢀlike form
C28H27F3NO6P, CCl4
715.29
1JHC = 161.2 Hz, 3JPNCC = 19.5 Hz, 3JHCCC = 5.0 Hz (d1, d2));
1
3
88.16 (ddt (d), C(6), JHC = 164.0 Hz, JPNCC = 17.5 Hz,
3JHCCC = 5.4 Hz); 88.09 (ddt (d), C(6), JHC = 164.0 Hz,
1
3JPNCC = 17.5 Hz, 3JHCCC = 5.4 Hz (d3, d4)); 78.88 (dq (dq), C(8),
Crystal system
Monoclinic
1JPC = 135.3 Hz, JFCC = 29.3 Hz (d1 + d2)); 80.16 (dq (dq),
2
Space group
P21/c
C(8), 1JPC = 142.7 Hz, JFCC = 30.5 Hz (d3, d4)); 62.94 (tq (s),
2
Parameters of unit cell
1
2
C(31), JHC = 149.1 Hz, JHCC = 4.5 Hz); 62.84 (tq (s), C(31),
1JHC = 149.1 Hz, 2JHCC = 4.5 Hz (d1, d2)); 63.40 (tq (s), C(31),
a/Å
b/Å
c/Å
8.8033(9)
19.658(2)
18.716(2)
95.414(1)
3224.5(6)
4
1.473
4.77
1464
1JHC = 149.5 Hz, 2JHCC = 4.5 Hz); 63.37 (tq (s), C(31), 1JHC
=
= 149.5 Hz, 2JHCC = 4.5 Hz (d3, d4)); 163.33 (br.m (dq), C(30),
2JPCC = 1.9—2.0 Hz, 3JFCCC = 1.9—2.0 Hz); 163.31 (br.m (dq),
/deg
V/Å3
2
3
C(30), JPCC = 1.9—2.0 Hz, JFCCC = 1.9—2.0 Hz (d1, d2));
164.02—164.05 (br.m (m), C(30), JPCC = 5.2 Hz, JFCCC
= 1.6 Hz (d3, d4)); 35.01 (m (s), C(15), 3JHC(10)CC(15) = 3.7 Hz,
3JHC(12)CC(15) = 3.7 Hz, 3JHCCC = 3.7 Hz); 34.83 (m (s), C(15),
3JHC(10)CC(15) = 3.7 Hz, 3JHC(12)CC(15) = 3.7 Hz, 3JHCCC = 3.7 Hz
(d1, d2)); 35.15 (m (s), C(15)); 34.85 (m (s), C(15) (d3, d4));
Z
2
3
=
dcalc/g cm–3
Absorption coefficient/Mo cm–1
F(000)
Number of measured reflections
Rint
7745
0.0420
5636
1
3
31.66 (q.sept (s), C(16)—C(18), JHC = 125.8 Hz, JHCCC
=
Number of observed independent
reflections with I > 2(I)
Divergence factor
values, I > 2(I)
1
= 4.8 Hz); 31.62 (q.sept (s), C(16)—C(18), JHC = 125.8 Hz,
3JHCCC = 4.8 Hz (d1, d2)); 31.67 (m (s), C(16)—C(18)); 31.52
(m (s), C(16)—C(18) (d3, d4)); 13.30 (qt (s), C(32), 1JHC = 127.6
Hz, JHCCC = 2.6 Hz); 13.27 (qt (s), C(32), JHC = 127.6 Hz,
3JHCCC = 2.6 Hz (d1, d2)); 13.75 (qt (s), C(32), 1JHC = 127.7 Hz,
3JHCCC = 2.7 Hz); 13.73 (qt (s), C(32), 1JHC = 127.7 Hz, 3JHCCC
= 2.7 Hz (d3, d4)); 127.65 (dm (s), C(24), C(28), JHC
= 160.3 Hz, JHCCC = 6.0—7.0 Hz, JHCCC = 6.0—7.0 Hz);
127.63 (dm (s), C(24), C(28), JHC = 160.3 Hz, JHCCC
= 6.0—7.0 Hz, JHCCC = 6.0—7.0 Hz (d1, d2)); 128.03 (C(24),
C(28), 1JHC = 160.4 Hz); 127.99 (dm (s), C(24), C(28), 1JHC
R = 0.0557,
Rw = 0.1434
0.896
3
1
GOOF
Number of refined parameters
Region of indices measurements
401
=
=
–11  h  11,
–25  k  25,
–24  l  24
1.007 and –1.134
1
3
3
1
3
=
Maximum and minimum
peaks/e Å–3
3
=

1096
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 4, April, 2013
Dimukhametov et al.
teractions were performed using the PLATON14 and ORTEP15
programs. The single crystal of compound 3b was studied in the
Community Federal Spectroꢀanalytical Center of the A. E. Arbuꢀ
zov Institute of Organic and Physical Chemistry Kazan Scientific
Center of the Russian Academy of Sciences, the Laboratory of
Diffractional Methods of Study. Crystallographic characteristics
of compound, parameters of experiment and refinement of the
structure are given in Table 2.
Yu. Yu. Kotorova, I. V. Konovalova, Phosphorus. Sulfur,
Silicon. Relat. Elem., 2008, 183, 425; (d) L. M. Abdrakhꢀ
manova, V. F. Mironov, T. A. Baronova, D. B. Krivolapov,
I. A. Litvinov, M. N. Dimukhametov, R. Z. Musin, A. I.
Konovalov, Russ. Chem. Bull. (Int. Ed.), 2008, 57, 1559 [Izv.
Akad. Nauk, Ser. Khim., 2008, 1528]; (e) V. F. Mironov,
Yu. Yu. Kotorova, L. M. Burnaeva, A. A. Balandina, Sh. K.
Latypov, A. B. Dobrynin, A. T. Gubaidullin, I. A. Litvinov,
R. Z. Musin, I. V. Konovalova, Mendeleev Commun., 2009,
19, 34; (f) V. F. Mironov, Yu. Yu. Borisova, L. M. Burnaeva,
A. T. Gubaydullin, A. B. Dobrynin, I. A. Litvinov, R. Z.
Musin, I. V. Konovalova, Russ. Chem. Bull. (Int. Ed.), 2010,
59, 820 [Izv. Akad. Nauk, Ser. Khim., 2010, 804]; (g) M. N.
Dimukhametov, L. M. Abdrakhmanova, V. F. Mironov,
R. Z. Musin, Zh. Obshch. Khim., 2010, 80, 1752 [Russ. J.
Gen. Chem. (Engl. Transl.), 2010, 80, 1752]; (h) L. M. Abꢀ
drakhmanova, V. F. Mironov, T. P. Gryaznova, S. A. Katꢀ
syuba, M. N. Dimukhametov, Phosphorus, Sulfur, Silicon.
Relat. Elem., 2011, 186, 652.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 10ꢀ03ꢀ
00525a).
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7. (a) L. M. Abdrakhmanova, V. F. Mironov, T. A. Baronova,
M. N. Dimukhametov, D. B. Krivolapov, I. A. Litvinov,
A. A. Balandina, Sh. K. Latypov, A. I. Konovalov, Menꢀ
deleev Commun., 2006, 16, 320; (b) L. M. Abdrakhmanova,
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Krivolapov, I. A. Litvinov, R. Z. Musin, A. I. Konovalov,
Mendeleev Commun., 2007, 17, 284; (c) V. F. Mironov, L. M.
Burnaeva, L. M. Abdrakhmanova, M. N. Dimukhametov,
Received January 9, 2013;
in revised form March 7, 2013