3,3-Bis(Diethylphosphono)-1(3H)- isobenzofuranone and its properties

Article abstract of DOI:10.1080/10426507.2010.508064

The reaction of o-phthaloyl chloride with sodium diethylphosphite led to the formation of new 3,3-bis(diethylphosphono)-1-(3H)-isobenzofurane 1. The reaction of bisphosphonate with alkylamine occurs with replacement of an ester oxygen by an imine group to

Full text of DOI:10.1080/10426507.2010.508064

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Phosphorus, Sulfur, and Silicon and the
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3,3-Bis(diethylphosphono)-1(3H)-
isobenzofuranone and Its Properties
V. N. Zemlianoy a , A. O. Kolodiazhna a , A. V. Gutov a , A. N.
Chernega a , V. P. Kukhar a & O. I. Kolodiazhnyi a
a Institute of Bioorganic Chemistry and Petroсhemistry , National
Academy of Sciences of Ukraine , Kyiv , Ukraine
Published online: 25 Apr 2011.
To cite this article: V. N. Zemlianoy , A. O. Kolodiazhna , A. V. Gutov , A. N. Chernega , V. P.
Kukhar & O. I. Kolodiazhnyi (2011) 3,3-Bis(diethylphosphono)-1(3H)-isobenzofuranone and Its
Properties, Phosphorus, Sulfur, and Silicon and the Related Elements, 186:4, 772-774, DOI:
10.1080/10426507.2010.508064
To link to this article: http://dx.doi.org/10.1080/10426507.2010.508064
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Phosphorus, Sulfur, and Silicon, 186:772–774, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.508064
3,3-BIS(DIETHYLPHOSPHONO)-1(3H)-
ISOBENZOFURANONE AND ITS
PROPERTIES
V. N. Zemlianoy, A. O. Kolodiazhna, A. V. Gutov,
A. N. Chernega, V. P. Kukhar, and O. I. Kolodiazhnyi
Institute of Bioorganic Chemistry and Petroсhemistry, National Academy
of Sciences of Ukraine, Kyiv, Ukraine
Abstract The reaction of o-phthaloyl chloride with sodium diethylphosphite led to the
formation of new 3,3-bis(diethylphosphono)-1-(3H)-isobenzofurane 1. The reaction of bis-
phosphonate with alkylamine occurs with replacement of an ester oxygen by an imine group
to afford the crystalline isoindolyl-bis-phosphonate—a representative of this new type of
organophosphorus heterocycles.
Keywords Bisphosphonates; bisphosphonic acid; isobenzofurane derivatives; o-phthalyl chlo-
ride
The reaction of o-phthalyl chloride with sodium diethylphosphite occurs with the formation
of cyclic bisphosphonate, 3,3-bis(diethylphosphono)-1-(3H)-isobenzofuranone 1. In the
first step of the reaction, the nucleophilic attack of sodium diethylphosphite on the С О
group of phthalic chloride gives the ketophosphonate A, which in the second step reacts
with the second molecule of sodium diethylphosphite being converted into intermediate B,
which via the intramolecular cyclization yields isobenzofuranone 1 (Scheme 1).
O
O
O
O
O
O
O
O
(EtO)2P
P(OEt)2
O
P(OEt)2
(EtO)2P
(EtO)2PONa
(EtO)2PONa
Cl
Cl
ONa
Cl
P(OEt)2
Cl
O
–NaCl
O
O
A
B
1
Scheme 1
The structure of bisphosphonate 1 was confirmed by NMR, mass spectra, IR spectra,
X-ray analysis (Figure 1),1 elemental analysis, and chemical reactions.
The signal δP of cyclic compounds 1 is shifted to a weak field in comparison with
acyclic compounds and is revealed at 10 ppm. In the 13С-NMR spectrum of bisphosphonate
Received 7 July 2010; accepted 8 July 2010.
Address correspondence to O. I. Kolodiazhni, Institute of Bioorganic Chemistry and Petroсhemistry, National
Academy of Sciences of Ukraine, Murmanskaia Str., 1, Kyiv 02094, Ukraine. E-mail: olegkol321@rambler.ru
772

3,3-BIS(DIETHYLPHOSPHONO)-1(3H)-ISOBENZOFURANONE
773
Figure 1 X-ray structure of 1.
1 the signal of the α-carbon atom between two phosphorus is observed as a triplet at 83.26
1
ppm, JPC = 155.9 Hz, which confirms the presence of a 1,1-bisphosphonate fragment.2
The ethoxy groups at phosphorus are nonequivalent, which is indicated by their various
disposition relative (over and out) to the benzene ring. The chemical properties of bisphos-
phonate 1 confirm its structure. A reflux with aqueous potash resulted in the elimination of
one diethylphosphonate group and led to the formation of acyclic 1-ketophosphonate 2 in a
good yield. The hydrolysis of bisphosphonate 1 with hydrochloric acid led to the formation
of bisphosphonic acid 3 in good yield (Scheme 2).3
O
O
P(O)(OEt)2
O
(HO)2P(O)
P(O)(OH)2
(EtO)2P
P(OEt)2
K2CO3/H2O
HCl/H2O
O
O
CO2H
O
O
2
1
3
Scheme 2
The reaction of bisphosphonate 1 with benzylamine in the presence of triethylamine
resulted in the formation of new organophosphorus heterocycle, phthalimide 4.3 The re-
action proceeds via nucleophilic substitution at the С О group and the formation of
α-hydroxybisphosphonate intermediate (D), which was registered by 31Р-NMR spectra
(signal δP +18.09 ppm). Then this intermediate (D) undergoes intramolecular cyclization
with the formation of phthalimide 4. The spectroscopic data of compound 4 are similar to

774
V. N. ZEMLIANOY ET AL.
(EtO)2P(O)
(EtO)2P(O)
P(O)(OH)2
(EtO)2P(O)
P(O)(OEt)2
H3O+
(HO)2P(O)
P(O)(OEt)2
P(O)(OEt)2
BnNH2
OH
N
NBn
O
NHBn
Ph
–H2O
O
O
O
O
1
D
4
5
Scheme 3
that of compound 1; in particular, the chemical shift δP is also shifted into a lower field
(6 ppm). The 1Н-NMR spectrum shows the presence of conformers of compound 4 because
of the effect of the NBn group. The 13С-NMR spectrum shows the signals of the СН3 and
СН2О groups, the singlet of the СН2Ph group at 43.16 ppm, the double doublet of Р-С
group with a coupling constant J = 150 Hz, the singlet of C O group, δC 170.55 ppm,
and signals of aromatic carbons.3 The bisphosphonate 4 is readily hydrolyzed by conc.
hydrochloric acid with the formation of bisphosphonic acid 5 (Scheme 3).
REFERENCES
1. Guenin, E.; Degache, E.; Liquier, J.; Lecouvey, M. Eur. J. Org. Chem. 2004, 2983–2987.
2. Quin, L. D. A Guide to Organophosphorus Chemistry; Wiley: New York, 2000, p. 151.
3. Zemlianoy, V. N.; Chernega, A.; Gutov, A. V.; Kolodiazhna, A. O.; Kolodiazhnyi, O. I. Phosphorus,
Sulfur Silicon Relat. Elem. 2011, 186, 481–488.