An unusual reaction of triphenylphosphine with dichlorodinitrobenzofuroxan

Article abstract of DOI:10.1080/10426500902719636

A novel phosphorylation reaction of dichlorodinitrobenzofuroxan by triphenylphosphine has been studied. An unusual course of the reaction with the participation of benzofuroxan nitro groups as reactive centers has been established. It is shown that as fin

Full text of DOI:10.1080/10426500902719636

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Phosphorus, Sulfur, and Silicon
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An Unusual Reaction of
Triphenylphosphine with
Dichlorodinitrobenzofuroxan
a
a
Irina V. Galkina , Elena V. Tudriy , Olga N.
a b
a
Kataeva
, Luiza M. Yusupova , Heinrich
c
a
Luftmann & Vladimir I. Galkin
a
A. M. Butlerov Chemistry Institute of the Kazan
State University , Kazan, Russia
b
A. E. Arbuzov Institute of Organic and Physical
Chemistry of the Russian Academy of Sciences ,
Kazan, Russia
c
Institute of Organic Chemistry, University of
Münster , Münster, Germany
Published online: 26 Mar 2009.
To cite this article: Irina V. Galkina , Elena V. Tudriy , Olga N. Kataeva , Luiza M.
Yusupova , Heinrich Luftmann & Vladimir I. Galkin (2009) An Unusual Reaction of
Triphenylphosphine with Dichlorodinitrobenzofuroxan, Phosphorus, Sulfur, and Silicon
and the Related Elements, 184:4, 987-991, DOI: 10.1080/10426500902719636
To link to this article: http://dx.doi.org/10.1080/10426500902719636
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Phosphorus, Sulfur, and Silicon, 184:987–991, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500902719636
An Unusual Reaction of Triphenylphosphine
with Dichlorodinitrobenzofuroxan
1
1
1,2
Irina V. Galkina, Elena V. Tudriy, Olga N. Kataeva,
1
3
Luiza M. Yusupova, Heinrich Luftmann,
and Vladimir I. Galkin
A. M. Butlerov Chemistry Institute of the Kazan State University,
Kazan, Russia
1
1
2
A. E. Arbuzov Institute of Organic and Physical Chemistry of the
Russian Academy of Sciences, Kazan, Russia
3
Institute of Organic Chemistry, University of M u¨ nster, M u¨ nster,
Germany
A novel phosphorylation reaction of dichlorodinitrobenzofuroxan by triphenylphos-
phine has been studied. An unusual course of the reaction with the participation
of benzofuroxan nitro groups as reactive centers has been established. It is shown
that as final product of the reaction, a stable diphenolate diphosphabetaine with
strong participation of the mesomeric ketoylide structure is formed. The structure
of the product has been confirmed by X-ray diffraction.
Keywords Dichlorodinitrobenzofuroxan; NO generation; phosphorylation; triph-
enylphosphine
INTRODUCTION
5
,7-Dichloro-4,6-dinitrobenzofuroxan (1) is a highly reactive system
containing the electrophilic benzofuroxan cycle, which is prone to nu-
cleophilic substitution, owing to the presence of electron-acceptor sub-
stituents and easy leaving groups. In particular, the reactions of chlo-
rine substitution by various amines have been frequently investigated.1
It is essential that amination products as well as initial furoxane 1
Received 28 December 2007; accepted 31 January 2008.
Dedicated to Professor Marian Mikołajczyk from the CBMiM PAN in Ł o´ d z´ , Poland,
on the occasion of his 70th birthday.
The authors are thankful to Dr. Roland Fr o¨ hlich for providing the opportunity to carry
out a single crystal X-ray diffraction experiment at the University of M u¨ nster.
Address correspondence to Vladimir I. Galkin, A. M. Butlerov Chemistry Insti-
tute of the Kazan State University, Kremlevskaya 18, Kazan 420008, Russia. E-mail:
vig54@mail.ru
987

988
I. V. Galkina et al.
possess pronounced antibacterial and fungicidal activity.2,3 Introduc-
tion of biogenic organophosphorus substituents to the benzofuroxan
ring might even increase the activity of these compounds; however, no
data on the phosphorylation of benzofuroxan is available in the litera-
ture until now.
RESULTS AND DISCUSSION
In this article, we report the interaction of benzofuroxan 1 with triph-
enylphosphine. The reaction proceeds readily at room temperature to
give the bisphosphorylation product, the ratio of 1 to triphenylphos-
phine being 1:2.5. The reaction most probably is not a simple nucle-
ophilic substitution, as it does not stop upon the formation of 5,7-
(
bis-triphenylphosphonio)-4,6-dinitrobenzofuroxanyldichloride (2), but
rather continues with the elimination of two nitrogen oxide and chlo-
rine molecules, as is shown in Scheme 1. The final product 3 can be
described by a series of mesomeric structures.
Cl
O
Ph3P
Cl
O
O
O N
2
N
N
N
N
N
Ph3P
+
O
O
O
Cl
Ph3P
NO2
N
2
1
Cl
O
O
Ph3P
Ph3P
Ph3P
O
O
O
N
N
N
N
N
O
O
O
O
O
N
Ph3P
Ph3P
Ph3P
O
O
O
O
3
Cl2
+
2Cl N=O
2
NO
SCHEME 1 Phosphorylation of benzofuroxan 1.
The structure of 3 has been determined by X-ray single-crystal
diffraction (Figure 1) and mass spectrometry.
The distribution of the bond lengths shows that the molecular struc-
ture of 3 in crystal is closer to the ylide mesomeric form. The average
value for the ylide P C bond (1.72 Å) derived from the Cambridge

Reaction of PPh with Dichlorodinitrobenzofuroxan
989
3
FIGURE 1 Molecular structure of 3 in the crystal. Selected bond lengths: C1A-
C5A 1.47(1), C1A-C5B 1.447(8), C5A-C6A 1.431(6), C5B-C6B 1.432(6), C6A-
C7 1.457(5), C6B-C7 1.441(6), C7=O7 1.259(4), P9-C6A 1.70(1), P-Ph(average)
1
.809(3) Å.
4
Crystallographic Database is the same within experimental errors
as in compound 3. The C O bonds are slightly elongated, while the
C-C bonds in the benzo-ring are shorter than typical C-C bonds. The
molecule lies on a special position on a symmetry plane m, implying
the symmetrical positions of the triphenylphosphine groups and the
disorder of the furoxan cycle. The latter causes low accuracy of the
geometrical parameters. The cavity between the triphenylphosphine
substituents is filled with disordered water molecules which are bound
to the C O and N→O bonds of the neighboring molecules via hydrogen
bonds.
In the mass spectrum (ESI-MS positive), the observed peak at m/z
89 corresponds to the protonated molecule C42H31N2O4P2 [M + H ].
+
6
EXPERIMENTAL
Compound 3
To a solution of Ph3P (1.64 g, 6.25 mmol) in 10 mL of 1:1 (in
volume) mixture of EtOH and Et2O, a solution of 5,7-dichloro-4,

990
I. V. Galkina et al.
6
-dinitrobenzofuroxan (0.73 g, 2.5 mmol) was added dropwise in 20 mL
of the same solvent mixture. The reaction mixture was stirred un-
der argon atmosphere for 2.5 h at r.t. After 2 months, the precipi-
tate was collected by filtration, washed with the same solvent mixture
(
2 × 30 mL), and dried in vacuo, affording compound 3 as a white
◦
31
solid; 1.28 g (75%). DSC/TG: mp 235 C (dec.). P NMR (DMSO-d6): δ =
3.7 (s). ESI-MS: Mass spectra were measured with a Quattro LCZ
Waters-Micromass, Manchester, UK) with nanospray inlet. ESI-MS
2
(
positive: The observed peak at m/z 689 corresponds to the protonated
+
molecule C42H31N2O4P2 [M + H ]. Anal. Calcd. for C42H30N2O4P2:
C, 73.26; H, 4.36; N, 4.07; P, 9.01. Found: C, 73.33; H, 4.27; N, 4.21;
P, 9.36.
X-Ray Structure Determination
Data were collected with Nonius Kappa CCD diffractometer equipped
with a rotating anode generator Nonius FR591. Programs used: data
5
collection COLLECT (Nonius B.V., 1998), data reduction Denzo-SMN,
6
7
absorption correction Denzo, structure solution SHELXS-97, struc-
ture refinement by full-matrix least-squares against F using SHELXL-
7, and the absolute configuration was assessed by Flack’s enan-
2
8
9
tiopole parameter. CCDC 652720 contains the supplementary crys-
tallographic data for this article. These data can be obtained free
of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: +44(1223)336033, E-mail: deposit@ccdc.cam.ac.
uk].
X-Ray Crystal Data for 3
Formula C42H30N2O4P2 H2O, M = 706.64, colorless crystal 0.35 ×
0
.30 × 0.06 mm, a = 20.5066(5), b = 9.9288(2), c = 9.1246(1) Å,
3
−3
−1
V = 1857.82(6) Å , ρcalc = 1.263 g cm , µ = 0.164 mm , empiri-
cal absorption correction (0.945 ≤ T ≤ 0.990), Z = 2 (molecule in a
special position on plane m), orthorhombic, space group Pmn21 (No.
3
1), λ = 0.71073 Å, T = 198 K, ω and ϕ scans, 24053 reflections
−1
collected (± h, ± k, ± l), [(sinθ)/λ] = 0.66 Å , 4357 independent
(
Rint = 0.073) and 3316 observed reflections [I ≥ 2 σ(I)], 268 refined
parameters, R = 0.055, wR2 = 0.134, max. residual electron density
3
0
.75 (–0.31) e Å , hydrogen atoms calculated and refined as riding
atoms.

Reaction of PPh with Dichlorodinitrobenzofuroxan
991
3
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