Reaction of 2-chloro-1,3,2-benzodioxaphosphinin-4-one with 2-(arylmethylideneamino)phenols. Stereoselective formation of 10-aryl-3,4: 8,9-dibenzo-5,7-dioxa-1-aza-6-phosphabicyclo[4.3.1]decane-2,6-diones

Full text of DOI:10.1134/S1070428014040290

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 4, pp. 605–607. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © M.N. Dimukhametov, G.A. Ivkova, V.F. Mironov, P.P. Onys’ko, Yu.V. Rassukanaya, R.Z. Musin, 2014, published in Zhurnal
Organicheskoi Khimii, 2014, Vol. 50, No. 4, pp. 616–618.
SHORT
COMMUNICATIONS
Reaction of 2-Chloro-1,3,2-benzodioxaphosphinin-4-one
with 2-(Arylmethylideneamino)phenols. Stereoselective
Formation of 10-Aryl-3,4 : 8,9-dibenzo-5,7-dioxa-1-aza-
6-phosphabicyclo[4.3.1]decane-2,6-diones
M. N. Dimukhametova, G. A. Ivkovaa, b, V. F. Mironova, b, P. P. Onys’koc,
Yu. V. Rassukanayac, and R. Z. Musina
a Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
e-mail: mironov@iopc.ru
b Kazan (Volga Region) Federal University, ul. Kremlevskaya 18, Kazan, 420008 Tatarstan, Russia
c Institute of Organic Chemistry, National Academy of Sciences of Ukraine,
ul. Murmanskaya 5, Kiev, 02660 Ukraine
Received January 23, 2014
DOI: 10.1134/S1070428014040290
Cyclic mixed anhydrides derived from hydroxy
carboxylic and phosphorous acids (2-R-1,3,2-benzodi-
oxaphosphinin-4-ones or “salicyl phosphites”) contain
a highly reactive macroergic POC(O) moiety and are
convenient intermediate products for regio- and stereo-
selective syntheses of various phosphorus-containing
heterocyclic (including bridged polycyclic) systems
which are difficult to obtain by other methods [1–4].
salicyl phosphite possessing a 2-(benzylideneamino)-
ethoxy group [5]. In the present communication we
describe intramolecular cyclization processes in the
system 2-chloro-1,3,2-benzodioxaphosphinin-4-one
(I)–2-(arylmethylideneamino)phenol II in the absence
of a base. Taking into account lower nucleophilicity of
the nitrogen atom in aromatic Schiff bases and con-
formational rigidity of the aromatic ring, which should
not favor intramolecular cyclization, we believed that
the imine fragment in initially formed phosphite III
(THF, 20°C) may act as a base. However, we failed to
We previously reported on stereoselective synthesis
of a 1,4,2-benzoxazaphosphepine derivative via intra-
molecular expansion of the six-membered ring in
O
Cl
O
O
P
P
OH
N
O
O
P
O
O
+
HN
NH
Cl–
O
Ar
O
O
Cl–
Ar
Ar
I
IIa, IIb
IIIa, IIIb
A
O
O
P
5O
O
7
O
6
14
O
P
13
12
Ar
15
17
4
8
10
3
N
O
2
16
N
H
9
Ar
11
1
Cl
18
O
Va, Vb
IVa, IVb
R = Ph (a), naphthalen-2-yl (b).
605

DIMUKHAMETOV et al.
606
3
4
3JHH = 7.2), 7.54 d.d.d.d (13-H, JHH = 7.6, 8.4, JHH
=
detect intermediate III in the reaction mixture. After
treatment of the reaction mixture with triethylamine in
the final step, we isolated the corresponding intra-
molecular cyclization products, stable cage-like phos-
phorus-containing heterocycles, 10-aryl-3,4:8,9-diben-
zo-5,7-dioxa-1-aza-6-phosphabicyclo[4.3.1]decane-
2,6-diones IV, which were formed as the only dia-
stereoisomer. A probable reaction scheme includes
transformation of initially formed phosphite III into
quasiphosphonium salt A which is readily converted
into 3,4-dihydro-2H-1,4,2λ5-benzoxazaphosphinine V
with a 2-chlorocarbonylphenoxy substituent on the
phosphorus atom via the Arbuzov reaction. The
31P NMR spectra of compounds Va and Vb contained
doublet signals at δP 12.0 (2JPH = 15.7 Hz) and
11.9 ppm (2JPH = 14.7 Hz), respectively. Addition of
triethylamine promotes cyclization of V to cage-like
heterocycles IV.
1.7, 5JHP = 1.4), 7.65 d.d (15-H, 3JHH = 7.7, 4JHH = 1.9),
7.76 d.d (11-H, 3JHH = 7.6, 4JHH = 1.7). 13C–{1H} NMR
spectrum, δC, ppm (J, Hz): 50.62 d (C10, 1JCP = 125.2),
118.37 d (C14, JCP = 6.6), 121.67 d (C15, JCP = 4.0),
3
3
124.35 s (C18), 125.38 d (Ci, JCP = 6.1), 125.89 d (C3,
2
3JCP = 1.8), 126.92 d (C16, JCP = 1.6), 127.40 d (Co,
4
3JCP = 7.7), 128.25 d (C12, JCP = 2.2), 128.64 s (Cp),
5
128.73 s (Cm), 128.92 d (C9, JCP = 5.5), 128.98 (C17),
2
130.50 s (C11), 134.35 s (C13), 146.33 d (C8, JCP
=
=
=
2
11.9), 147.29 d (C4, JCP = 8.0), 168.12 d (C2, JCP
2
3
1.6). 31P NMR spectrum: δP 11.6 ppm, d (2JPH
14.7 Hz). MALDI mass spectrum: m/z 364 [M + H]+.
ESI mass spectrum: m/z 364 [M + 1]+. Found, %:
C 65.71; H 3.67; N 4.10; P 8.15. C20H14NO4P. Cal-
culated, %: C 66.12; H 3.86; N 3.86; P 8.54.
3,4:8,9-Dibenzo-10-(2-naphthyl)-5,7-dioxa-
1-aza-6-phosphabicyclo[4.3.1]decane-2,6-dione
(IVb) was synthesized in a similar way. Yield 78%,
light yellow powder, mp 123°C. IR spectrum, ν, cm–1:
1
The structure of compounds IV was proved by H,
13C, and 31P NMR, IR, and MALDI and ESI mass
1
1689 (C=O), 1290 (P=O). H NMR spectrum, δ, ppm
1
spectra. In the H NMR spectra of IVa and IVb we
2
(J, Hz): 5.92 d (10-H, JHP = 14.1), 7.05 br.d.d (18-H,
observed a doublet signal in the region δ 5.7–5.9 ppm
(2JPH = 14.7 Hz), corresponding to the PCHN proton;
the same coupling constant was found for the phos-
phorus signal. The mass spectra of IVa and IVb
contained strong peaks of their molecular ions with
m/z 363 and 413, respectively.
3JHH = 8.0, JHH = 1.7), 7.12–7.15 m (16-H, 17-H),
4
7.43–7.45 m and 7.71–7.75 m (13-H, C10H7), 7.56 br.d
3
3
(14-H, JHH = 8.4), 7.63 br.d.d (12-H, JHH = 7.6, 7.6),
7.89 d.d (15-H, 3JHH = 7.6, 4JHH = 1.9), 8.00 br.d (11-H,
3JHH = 8.0). 13C–{1H} NMR spectrum, δC, ppm (J, Hz):
51.09 d (C10, JCP = 125.6), 118.81 d (C14, JCP = 6.6),
1
3
121.98 d (C15, JCP = 4.3), 124.59 s (C18), 124.59 d
3
3,4:8,9-Dibenzo-10-phenyl-5,7-dioxa-1-aza-
6-phosphabicyclo[4.3.1]decane-2,6-dione (IVa).
A solution of 4.61 g (23.40 mmol) of aminophenol IIa
in 25 mL of anhydrous THF was added dropwise over
a period of 30 min under stirring at 20°C in an argon
atmosphere to a solution of 4.74 g (23.40 mmol) of
compound I in 20 mL of anhydrous THF. The mixture
was stirred for 30 min, 2.60 g (25.74 mmol) of
triethylamine was added dropwise over a period of
10 min (20°C), and the mixture was stirred for 1 h and
left overnight. The precipitate was filtered off, the
solvent was removed under reduced pressure, and the
residue, a light brown oily liquid, was treated with
anhydrous diethyl ether to obtain a light gray powder.
The product was filtered off, washed with diethyl
ether, and dried under reduced pressure. Yield 6.37 g
(75%), mp 117°C. IR spectrum, ν, cm–1: 1694 (C=O),
1285 (P=O). 1H NMR spectrum, δ, ppm (J, Hz): 5.73 d
3
2
(C1′, JCP = 9.3), 125.29 d (C2′, JCP = 6.1), 126.08 d
(C3, 3JCP = 1.9), 126.72 s (C6′), 126.99 s (C7′), 127.17 d
(C16, JCP = 1.1), 127.60 s (C8′), 127.24 d (C3′, JCP
=
4
3
6.4), 128.32 s (C5′), 128.54 d (C12, JCP = 2.1), 129.00
5
(C17), 129.15 s (C4′), 130.73 d (C11, JCP = 1.2),
4
132.90 s (C8a′), 132.97 s (C4a′), 133.18 d (C9, JCP
=
2
5.2), 134.62 s (C13), 146.65 d (C8, JCP = 11.9),
2
147.58 d (C4, JCP = 8.1), 168.39 d (C2, JCP = 1.7).
31P NMR spectrum: δP 11.4 ppm, d (2JPH = 14.1 Hz).
MALDI mass spectrum: m/z 414 [M + H]+. ESI mass
spectrum: m/z 414 [M + 1]+. Found, %: C 69.27;
H 4.19; N 3.49; P 7.68. C24H16NO4P. Calculated, %:
C 69.73; H 3.87; N 3.39; P 7.59.
2
3
The 1H, 31P, and 13C NMR spectra were recorded on
a Bruker Avance-400 spectrometer at 400, 162.0, and
100.6 MHz, respectively, using CDCl3 as solvent and
reference for H and 13C; the 31P chemical shifts were
1
2
3
4
(10-H, JHP = 14.8), 6.97 d.d (18-H, JHH = 8.0, JHH
=
measured relative to H3PO4 (external reference). The
IR spectra were recorded on a Bruker Vector-22
spectrometer from samples dispersed in mineral oil
and placed between KBr plates. The MALDI (matrix-
assisted laser desorption/ionization) mass spectra were
3
4
1.7), 7.07 d.d.d (16-H, JHH = 7.7, 7.7, JHH = 1.7),
7.12 d.d.d.d (17-H, JHH = 8.0, 7.7, JHH = 1.9, JHP
3
4
5
=
=
3
1.4), 7.14–7.16 m (m-H, p-H), 7.29 br.d (14-H, JHH
8.4), 7.33 br.d.d (12-H, 3JHH = 7.6, 7.6), 7.48 br.d (o-H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 4 2014

REACTION OF 2-CHLORO-1,3,2-BENZODIOXAPHOSPHININ-4-ONE
607
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obtained on a Bruker Ultraflex time-of-flight mass
spectrometer. The ESI (electrospray ionization) mass
spectra were obtained on a Bruker Daltonik Amazon
instrument with positive ion detection.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 13-03-90419).
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 4 2014