Rearrangement of O,O'-bis(2-benzylideneaminophenyl) phenylphosphonite into 1,6,7-triphenyl-3,4:9,10-dibenzo-2,11-dioxa-5,8-diaza-1-phosphatricyclo[6.3.0. 01,5]undeca-3,9-diene

Article abstract of DOI:10.1016/j.mencom.2012.03.016

Keeping of O,O'-bis(2-benzylideneaminophenyl) phenylphosphonite in a CCl4 solution for 50 days resulted in its spontaneous rearrangement into 1,6,7-triphenyl-3,4:9,10-dibenzo-2,11-dioxa-5,8-diaza-1-phosphatricyclo[6.3.0. 01,5]undeca-3,9-diene, a representative of spirophosphoranes with P-N bonds.

Full text of DOI:10.1016/j.mencom.2012.03.016

Mendeleev
Communications
Mendeleev Commun., 2012, 22, 98–100
Rearrangement of O,O'-bis(2-benzylideneaminophenyl)
phenylphosphonite into 1,6,7-triphenyl-3,4:9,10-dibenzo-
2,11-dioxa-5,8-diaza-1-phosphatricyclo[6.3.0.01,5]undeca-3,9-diene
Mudaris N. Dimukhametov, Vladimir F. Mironov,*
Dmitry B. Krivolapov, Igor A. Litvinov and Rashid Z. Musin
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre of the Russian Academy
of Sciences, 420088 Kazan, Russian Federation. Fax: +7 8432 75 5322; e-mail: mironov@iopc.ru
DOI: 10.1016/j.mencom.2012.03.016
Keeping of O,O'-bis(2-benzylideneaminophenyl) phenylphosphonite in a CCl4 solution for 50 days resulted in its spontaneous
rearrangement into 1,6,7-triphenyl-3,4:9,10-dibenzo-2,11-dioxa-5,8-diaza-1-phosphatricyclo[6.3.0.01,5]undeca-3,9-diene, a repre-
sentative of spirophosphoranes with P–N bonds.
Previously, we were the first to show that Piii derivatives con-
OH
PhPCl2 + 2 NEt3
taining unsaturated electrophilic groups as substituents, such as
2
– 2 Et3N · HCl
2-benzylideneaminophenyl, 3- or 4-oxo(imino)alkyl, react with
N
CHPh
a
ctivated carbonyl compounds under mild conditions with formation
of new P–C, P–O and P–N bonds to give cage phosphoranes.1–7
The interest in the chemistry of pentacoordinate phosphorus
derivatives is based on the key role of these compounds as inter-
mediates in phosphorylation and dephosphorylation, i.e., reac-
tions of primary importance for vital activity of cells.8–16
2
15
14
13
16
12–15
17
11
6
3
PhP
O
N
1
2
12
2
37
34
18
5
4
10
9
3
O
O
1
36
35
19
20
P
*
8
N
5
Taking into account that unsaturated compounds which are not
activated by acceptor substituents, including imines, hardly (if at
all) undergo these reactions, we made a first attempt to implement
an intramolecular version of cyclisation for Piii derivatives con-
taining two imino groups. One of them, O,O'-bis(2-benzylidene-
aminophenyl) phenylphosphonite 1, was synthesized using the
reaction of dichlorophenylphosphine with two equivalents of
2-benzylideneaminophenol 2 in the presence of triethylamine
(Scheme 1). The structure of compound 1 was confirmed by NMR
and mass spectra. The protons of the two N=CH groups manifest
4
N
21
24
8–11
7
* *
7
6
33
23
Ph
2
22
28
29
32
31
1
27
26
25
30
3a,b
Scheme 1
Synthesis of compound 1. Phenyldichlorophosphine (2.81 g, 15.70 mmol)
in 10 ml of CCl4 was added dropwise with stirring over 30 min (15–20°C)
under dry argon to a mixture of 2-benzylideneaminophenol 2 (6.18 g,
31.37 mmol) and triethylamine (3.17 g, 31.39 mmol) in 60 ml of freshly
distilled CCl4. After the entire amount of the reagent was added, the
reaction mixture was stirred for another 2 h and kept overnignt. Next day,
the precipitate of triethylammonium hydrochloride that formed was
filtered off and the filtrate was carefully concentrated in vacuo (0.1 Torr).
The resulting unstable oil of compound 1 was quickly characterised by
1
themselves in the H NMR spectrum as two main singlets with
d 8.38 and 8.39 in a ~1:4 ratio. The two singlets with dP 165.1
and 165.3 in the 31P-{1H} spectrum are present in approximately
the same ratio. Apparently, it is a manifestation of the syn/anti-
isomerism of the two imino groups. The electron impact mass
+
·
spectrum contains a 500 [M] molecular ion peak matching the
molecular mass of compound 1.†
1
spectral methods. H NMR (CCl4–CDCl3, 4:1) d: 8.39, 8.37, 8.25 (3s,
Monitoring of the behaviour of phenylphosphonite 1 in a
CCl4 solution by means of 31P-{1H} shows that two new peaks
at dP –22.7 and –23.7 appear in the spectrum and gradually grow,
whereas the intensity of the signal of compound 1 gradually
decreases. The conversion is completed within 50 days and the
N=CHPh, 4:1:0.03), 7.88 (br.dd), 7.67 (br.d), 7.38 (m), 7.32 (m), 7.24
(m), 7.10 (m), 7.04 (m) (PPh, C6H4, CPh). 13C NMR (main isomer,
CCl4–CDCl3, 4:1) d: 120.10 [dd (s), C3, 1JHC 160.0 Hz, JHC CC 8.4 Hz],
3
3
5
3
121.74 [ddddd (d), C6, JHC 160.4 Hz, JPOCC 7.5 Hz, JHC CC 7.3 Hz,
1
3
3
6
6
4
6
2
4
5 1
5
6
3
6
5
JHC C 1.6 Hz, JHC CCC 1.6 Hz], 124.08 [br.dd (br.s), C , JHC 161.4 Hz,
3
4
1
3
3
5
4
6
4
JHC CC 8.4 Hz], 126.83 [dm (s), C , JHC 161.5 Hz, JHC CC 8.4–9.8 Hz],
†
3
3
1H, 31P and 31P-{1H} NMR spectra were recorded on a Bruker Avance 400
127.92 [ddd (d), C14, 1JHC 160.8 Hz, JHC
7.0 Hz, JPCCC 5.6 Hz],
7.6 Hz], 129.35 [dm (s),
7.2–7.5 Hz, JHC CC 3.7 Hz,
14’CC14
10’CC10
11CC9
13
14
14
spectrometer (400 MHz for 1H; 161.9 MHz for 31P, 31P-{1H}; 100.6 MHz
for 13C, 13C-{1H}) (20°C, d scale with reference to Me4Si) with signals
for the residual protons of the deuterated solvent (CDCl3) or the carbon
nuclei as the internal standards (1H and 13C) and with H3PO4 as the
external standard (31P). IR spectra were recorded on a Bruker Vector 22
FTIR spectrometer in Nujol. The EI mass spectra were obtained on a DFS
Thermo Electron Corporation instrument (USA); the ionizing electron
energy was 70 eV; the ion source temperature was 290°C. A direct inlet
system was used. The evaporator tube was heated in the programmed
mode from 100 to 350°C. The processing of mass spectral data was
performed using Xcalibur software.
128.63 [br.dd (s), C10, 1JHC 160.0 Hz, JHC
3
10
C9, 1JHC 160.0 Hz, JHC
7.2–7.5 Hz, 3JHC
3
3
9’CC9
9
7
9
2
13
1
2
10C9
13
JHC 1.4 Hz], 130.81 [br.dddd (d), C , JHC 168.4 Hz, JPCC 21.6 Hz,
3JHC
7.2 Hz, 3JHC
7.2 Hz], 131.18 [dt (s), C , JHC 160.0 Hz,
11
1
13’CC13
15CC13
11
3
8
2
3
9
11
7 8
10CC8
14CC12
JHC CC 7.6 Hz], 136.70 [dtd (s), C , JHC C 11.2 Hz, JHC
7.2 Hz,
6.9 Hz,
4JHC
2JHC
1.0 Hz], 142.00 [dtdt (d), C , JPC 18.2 Hz, JHC
12
1
3
11CCC8
13C12
12
2
3
1.0 Hz, 4JHC
1.0 Hz], 143.37 [m (d), C , JPOCC 2.6 Hz],
15CCC12
2
149.33 [m (d), C1, JPOC 4.2 Hz], 160.57 [dt (s), C7, JHC 159.0 Hz,
2
1
1
7
JHC CC 5.0 Hz]. 31P-{1H} NMR (CCl4–CDCl3, 4:1) d: 165.1 and 165.3
3
9
7
+
+
·
·
(1:4). MS, m/z (%): 500 (100) [M] (C32H25N2O2P), 501 (35) [M] , 502
+
·
(6.6) [M] .
© 2012 Mendeleev Communications. All rights reserved.
– 98 –

Mendeleev Commun., 2012, 22, 98–100
ratio of the two signals of the final reaction products is 3:1.
C(16)
C(17)
C(15)
These reaction products, which are stable in the air, were found
to be two diastereomers of 1,6,7-triphenyl-3,4:9,10-dibenzo-
2,11-dioxa-5,8-diaza-1-phosphatricyclo[6.3.0.01,5]undeca-3,9-
diene 3a,b [d,l- (6,7-trans) and meso- (6,7-cis) forms].‡
C(14)
C(13)
C(12)
C(37)
C(10)
C(3)
C(19)
C(21)
O(11)
N(8)
Pure samples of the stereoisomers were obtained by column
chromatography separation on silica gel. Single crystals of the
d,l-form of compound 3a suitable for XRD were grown from a
CCl4 solution.§ Figure 1 shows the geometry of molecule 3a in
a crystal, along with selected parameters. An unusual feature of
the molecule is that the phosphorus atom has a distorted depressed
square pyramid configuration where two oxygen atoms and two
nitrogen atoms are arranged in the base of the pyramid, whereas
the phenyl substituent occupies the vertex. The base of the
pyramid (N8N5O2O11) is planar to within 0.058(2) Å; the P1 atom
deviates by 0.3917(6) Å from this plane. The angle between the
N8N5O2O11 and P1C12–17 planes is ~88.1°. The five-membered
P1N8C9C10O11 and P1N5C4C3O2 rings have a depressed envelope
conformation [the P1 atom deviates by 0.289(1) Å from the
O(2)
C(4)
C(18)
C(36)
P(1)
N(5)
C(6)
C(34)
C(20)
C(9)
C(35)
C(24)
C(7)
C(28)
C(33)
C(32)
C(31)
C(25)
C(26)
C(27)
C(29)
C(30)
Figure 1 Molecular structure and atom-labeling scheme for 3a (30%
thermal ellipsoids). Selected bond lengths (Å), bond and torsion angles (°):
P(1)–O(2) 1.673(2), P(1)–O(11) 1.694(2), P(1)–N(5) 1.720(2), P(1)–N(8)
1.698(2), P(1)–C(12) 1.807(3), O(2)–C(3) 1.379(3), O(11)–C(10) 1.375(3),
N(5)–C(4) 1.397(3), N(5)–C(6) 1.452(3), N(8)–C(7) 1.461(3), N(8)–C(9)
1.402(3), C(3)–C(4) 1.387(4), C(9)–C(10) 1.390(3); O(2)–P(1)–O(11)
84.10(9), O(2)–P(1)–N(5) 89.2(1), O(2)–P(1)–N(8) 149.1(1), O(2)–P(1)–
C(12) 102.3(1), O(11)–P(1)–N(5) 157.4(1), O(11)–P(1)–N(8) 88.43(9),
O(11)–P(1)–C(12) 98.53(9), N(5)–P(1)–N(8) 86.27(9), N(5)–P(1)–C(12)
104.0(1), N(8)–P(1)–C(12) 108.5(1), P(1)–O(2)–C(3) 114.2(2), P(1)–O(11)–
C(10) 113.3(2), P(1)–N(5)–C(4) 113.9(2), P(1)–N(5)–C(6) 121.1(2), P(1)–
N(8)–C(9) 114.4(2), N(5)–C(4)–C(3) 109.4(2), N(8)–C(7)–C(6) 104.9(2);
N(5)–P(1)–O(2)–C(3) 7.6(2), O(2)–P(1)–O(11)–C(10) –164.9(2), N(8)–
P(1)–O(11)–C(10) –14.9(2), O(2)–P(1)–N(5)–C(4) –6.0(2), N(8)–P(1)–
N(5)–C(6) 5.8(2), N(5)–P(1)–N(8)–C(7) –11.0(2), C(9)–N(8)–C(7)–C(6)
–171.9(2), P(1)–N(8)–C(7)–C(6) 12.6(3), N(5)–C(6)–C(7)–N(8) –6.9(3).
‡
Preparation of compound 3. A solution of compound 1 (7.85 g) in CCl4
(50 ml) was kept for 50 days at 20°C under dry argon. The solvent was
removed in vacuo; the residue was washed with 10 ml of a diethyl ether–
pentane mixture (1:1) and 10 ml of pentane, then kept under reduced
pressure (0.1 Torr) to give 7.25 g (92%) of a white powder as a mixture
of d,l- (3a) and meso- (3b) forms in 2.57:1 ratio. A sample of 3a,b was
chromatographed on silica gel in a benzene–hexane system (1:1). The com-
pounds were eluted in the order: d,l-form, meso-form. Individual samples of
both stereoisomers were isolated, mp 247–249°C (3a) and 345–346°C (3b).
3a: 1H NMR (CDCl3–CCl4, 3:1) d: 4.64 (dd, 1H, NCHPh, 3JPNCH 2.9 Hz,
3JHCCH 5.3 Hz), 4.83 (dd, 1H, NCHPh, 3JPNCH 11.6 Hz, 3JHCCH 5.3 Hz),
6.04 (d, 1H, H21, 3JH
7.8 Hz), 6.15 (d, 1H, H34, 3JH
7.7 Hz),
20CCH21
35CCH34
N8C9C10O11 plane; the O2 atom deviates by 0.105(2) Å from
the P1N5C4C3 plane; the O2C3C4N5 torsion angle is 2.7(3)°]. The
diazaphospholane P1N5C6C7N8 ring has an envelope conforma-
tion [the N8 atom deviates by –0.170(2) Å from the P1N5C6C7
plane; the N5C6C7N8 torsion angle is –6.9(3)°]. The phenyl groups
in the 1,3,2-diazaphospholane moiety are in a trans-configura-
tion (d,l-form) [the C22C6C7C28 torsion angle is 104.5(2)°]. It is
interesting to note that the aromatic protons of the two oxaza-
benzophosphole rings in the 1H NMR spectrum of this molecule
are pairwise nonequivalent, which is apparently due to the dif-
ferent anisotropic effect of the phenyls at C6,7 and at P1 and to the
presence of chiral centres (C6,7). The cis(meso) form 3b shows a
more symmetric picture, i.e., these protons are pairwise equivalent
(the anisotropic effects of the phenyls at C6,7 and at P1 on all
protons of both oxazabenzophosphole rings are the same).
The mechanism of this rearrangement remains an open issue.
A heterolytic mechanism can be suggested (Scheme 2) involving
an intramolecular attack of the phosphorus atom on one imino
group nitrogen followed by the formation of bipolar ion A.
Attack of the carbanion on the carbon atom of the second imino
group and formation of the second P–N bond result in the final
reaction product 3.
6.59 (dd, 1H, H19, 3JH
7.7 Hz, 3JH
7.5 Hz), 6.69 (dd, 1H, H36,
18CCH19
35CCH36
20CCH19
3JH
3JH
7.9 Hz, 3JH
7.5 Hz), 6.73 (dd, 1H, H20, 3JH
7.7 Hz,
7.5 Hz),
7.9 Hz),
16
37CCH36
19CCH20
21CCH20
7.8 Hz, 3JH
36CCH35
7.5 Hz), 6.83 (dd, 1H, H35, 3JH
34CCH35
6.88 (d, 1H, H18, 3JH
7.7 Hz), 6.94 (d, 1H, H37, 3JH
19CCH18
36CCH37
7.20–7.40 (m, 14H, 2Ph, H15), 7.39 (td, H16, 3JH
1.7 Hz), 7.54 (br.dd, H13, 3JPCCH 16.0 Hz, JH
7.2 Hz, JPCCCCH
5
15CCH16
14CCH13
3
7.1 Hz). 31P NMR
13
+
·
(CDCl3–CCl4, 3:1) d: –22.7. MS, m/z (%): 500 (100) [M] (C32H25N2O2P),
+
+
·
·
501 (35) [M] , 502 (6.6) [M] .
3b: 1H NMR (CDCl3–CCl4, 3:1) d: 5.25 (d, 2H, NCHPh, 3JPNCH 3.1 Hz,
3JHCCH 0 Hz), 6.29 (d, 2H, H21, JH
7.4 Hz), 6.74 (dd, 2H, H19,
3
20CCH21
overlaps with H23), 6.75 (br.d, 4H, H23, 3JH
7.7 Hz), 6.84 (dd, 2H,
24CCH23
3
3
3
H20, JH
7.9 Hz, JH
7.5 Hz), 6.91 (m, 4H, H24, JH
21CCH20
19CCH20
23CCH24
7.7 Hz, 3JH
2H, H18, 3JH
7.0 Hz), 6.95 (m, 2H, H25, 3JH
7.0 Hz), 7.09 (d,
25CCH24
19CCH18
24CCH25
7.8–7.9 Hz), 7.40 (m, 2H, H14, 3JH
7.5 Hz,
14CCH15
7.5 Hz,
15CCH14
3JH
7.2 Hz, JPCCCH 5.4 Hz), 7.51 (td, 1H, H , JH
4
15
3
13CCH14
14
JPCCCCH 1.7 Hz), 7.68 (br.dd, 2H, H13, JPCCH 16.4 Hz, 3JH
5
3
15
13
14CCH13
7.2 Hz). 31P NMR (CDCl3–CCl4, 3:1) d: –23.7. MS, m/z (%): 500 (100)
+
+
+
·
·
·
[M] (C32H25N2O2P), 501 (35) [M] , 502 (6.6) [M] .
§
Crystal data. Crystals of 3a (C32H25N2O2P, M = 500.51) are ortho-
rhombic, space group Pna21. At 293 K: a = 11.809(1), b = 22.751(3) and
1
c = 9.344(1) Å, V = 2510.4(5) Å3, Z = 4, dcalc = 1.324 g cm–3, m = 0.143 mm–
,
F(000) = 1048. Data were collected on a Bruker Smart APEX II CCD
automatic diffractometer [graphite monochromator, l(MoKa) = 0.71073 Å,
w-scanning], 2q < 52°, Rint = 0.0509. 18198 reflections were measured,
4495 of them were independent, the number of observed reflections with
I > 2s(I) was 3547, R = 0.0388, Rw = 0.0874, GOF = 1.028, the number
of refined parameters is 334. An absorption correction was performed using
SADABS program.17 The structure was solved by direct method using SIR
program18 and refined by the full matrix least-squares using SHELXL-97
program.19 Absolute structure was established [Flack parameter 0.05(9)].
All non-hydrogen atoms were refined anisotropically. All hydrogen atoms
were placed into the geometrically calculated positions and refined as riding
atoms. All calculations were performed using WinGX20 and APEX221
programs. All the figures and analysis of intermolecular interactions were
performed using PLATON22 and ORTEP23 programs.
Thus, the discovered rearrangement of O,O'-bis(2-benzylidene-
aminophenyl) phenylphosphonite may be considered as a new
Ph
O
O
N
N
_
O
N
Ph
Ph
Ph
3
Ph
P
+
P
N
Ph
O
CCDC 840832 contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
For details, see ‘Notice to Authors’, Mendeleev Commun., Issue 1, 2012.
A
1
Scheme 2
– 99 –

Mendeleev Commun., 2012, 22, 98–100
convenient and rather facile access to spirophosphoranes with
P–N bonds.
9 E. Marcos, M. J. Field and R. Crehuet, Proteins: Structure, Function and
Bioinformatics, 2010, 78, 2405.
10 N. J. Baxter, M. W. Bowler, T. Alizadeh, M. J. Cliff, A. M. Hounslow,
B. Wu, D. B. Berkowitz, N. H. Williams, G. M. Blackburn and J. P.
Waltho, Proc. Natl. Acad. Sci. U.S.A., 2010, 107, 4555.
11 H. Gao, Z. Ke, N. J. DeYonker, J. Wang, H. Xu, Z.-W. Mao, D. L. Phillips
and C. Zhao, J. Am. Chem. Soc., 2011, 133, 2904.
This study was supported by the Russian Foundation for
Basic Research (grant no. 10-03-00525).
12 T. Lönnberg and M. Laine, Org. Biomol. Chem., 2010, 8, 349.
13 K.-Y. Wong, T.-S. Lee and D. M.York, J. Chem. Theory Comput., 2011,
7, 1.
14 Y. Yamamoto, K. Nakao, T. Hashimoto, S. Matsukawa, N. Suzukawa,
S. Kojima and K.-y. Akiba, Heteroatom Chem., 2011, 22, 523.
15 E. Rosta, M. Nowotny, W. Yang and G. Hummer, J. Am. Chem. Soc.,
2011, 133, 8934.
16 E. P. A. Couzijn, J. C. Slootweg, A. W. Ehlers and K. Lammertsma,
J. Am. Chem. Soc., 2010, 132, 18127.
17 G. M. Sheldrick, SADABS, Bruker AXS Inc., Madison, USA, 1997.
18 A. Altomare, G. Cascarano, C. Giacovazzo and D. Viterbo, Acta Crystallogr.,
Sect. A, 1991, 47, 744.
19 G. M. Sheldrick, SHELX-97. Programs for Crystal Structure Analysis
(Release 97-2), University of Göttingen, 1997, vols. 1, 2.
20 L. J. Farrugia, J. Appl. Crystallogr., 1999, 32, 837.
21 APEX2 (Version 2.1), SAINTPlus. Data Reduction and Correction
Program (Version 7.31A), Bruker Advanced X-ray Solutions, Bruker
AXS Inc., Madison, Wisconsin, USA, 2006.
References
1 V. F. Mironov, T. A. Baronova, M. N. Dimukhametov, R. Z. Musin,
L. M. Abdrakhmanova and A. I. Konovalov, Zh. Obshch. Khim., 2006, 76,
515 (Russ. J. Gen. Chem., 2006, 76, 490).
2 L. M. Abdrakhmanova, V. F. Mironov, T. A. Baronova, M. N. Dimukhametov
D. B. Krivolapov, I. A. Litvinov, A. A. Balandina, Sh. K. Latypov and
A. I. Konovalov, Mendeleev Commun., 2006, 320.
3 L. M. Abdrakhmanova, V. F. Mironov, T. A. Baronova, M. N. Dimukhametov
D. B. Krivolapov, I. A. Litvinov, R. Z. Musin and A. I. Konovalov,
Mendeleev Commun., 2007, 17, 284.
,
,
4 V. F. Mironov, L. M. Burnaeva, L. M. Abdrakhmanova, M. N. Dimukhametov
Yu. Yu. Kotorova and I. V. Konovalova, Phosphorus Sulfur Silicon Relat.
Elem., 2008, 183, 425.
,
5 L. M. Abdrakhmanova, V. F. Mironov, T. A. Baronova, D. B. Krivolapov,
I. A. Litvinov, M. N. Dimukhametov, R. Z. Musin and A. I. Konovalov,
Izv. Akad. Nauk, Ser. Khim., 2008, 1528 (Russ. Chem. Bull., Int. Ed.,
2008, 57, 1559).
6 V. F. Mironov,Yu.Yu. Borisova, L. M. Burnaeva, A. T. Gubaidullin, A. B.
Dobrynin, I. A. Litvinov, R. Z. Musin and I. V. Konovalova, Izv. Akad.
Nauk., Ser. Khim., 2010, 804 (Russ. Chem. Bull., Int. Ed., 2010, 59,
820).
22 A. L. Spek, Acta Crystallogr., Sect. A, 1990, 46, 34.
23 L. J. Farrugia, J. Appl. Crystallogr., 1997, 30, 565.
7 L. M. Abdrakhmanova, V. F. Mironov, T. P. Gryaznova, S. A. Katsyuba
and M. N. Dimukhametov, Phosphorus Sulfur Silicon Relat. Elem., 2011,
186, 652.
8 A. Wittinghofer, Trends Biochem. Sci., 2006, 31 (1), 20.
Received: 4th August 2011; Com. 11/3777
– 100 –