A convenient synthesis of 2,7-Dioxa-5,10-diaza-3'5,8'5-diphospha-1,6(1,4)- dibenzenacyclodecaphanes

Full text of DOI:10.1134/S1070428012040331

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 4, pp. 622–624. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © M.N. Dimukhametov, V.F. Mironov, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 4, pp. 622–624.
SHORT
COMMUNICATIONS
A Convenient Synthesis of 2,7-Dioxa-5,10-diaza-
3λ5,8λ5-diphospha-1,6(1,4)-dibenzenacyclodecaphanes
M. N. Dimukhametov and V. F. Mironov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
e-mail: mironov@iopc.ru
Received August 4, 2011
DOI: 10.1134/S1070428012040331
Phosphorus-containing macrocyclic compounds
attract interest from the viewpoint of supramolecular
chemistry as model structures for studying molecular
recognition and complexation processes. Therefore,
much attention is given to the development of methods
of synthesis of such compounds [1–7].
We previously showed for the first time [8] that
p-(benzylideneamino)phenol in the absence of other
bases reacts with dialkyl phosphorochloridites in
chloroform to give phosphorus-containing [4.4]para-
cyclophane analogs. The present communication
reports on the results of analogous reactions with sub-
stituted iminophenols both in the absence (Scheme 1)
and in the presence of other base (Scheme 2).
of 1:1 (20°C, CHCl3) was carried out in an argon at-
mosphere (Scheme 1). If no other base was added, the
reaction was accompanied by separation of some solid
from the reaction mixture. Analogous pattern was ob-
served previously in the reaction of 4-(benzylidene-
amino)phenol with dialkoxy(chloro)phosphines [8].
1
On the basis of the H NMR data and elemental
analysis, the precipitate was identified as iminophenol
hydrochloride I′a or I′b. Thus in the absence of other
base, both phosphites IIa and IIb and initial imino-
phenols Ia and Ib act as acceptors of hydrogen
chloride liberated during the process. The most prob-
able way of formation of [4.4]paracyclophanes Va and
Vb involves initial generation from diethyl phos-
phorochloridite and iminophenol I of iminium salts III
which undergo cyclization to macrocyclic quasiphos-
The reaction of diethyl phosphorochloridite with
4-(arylmethylideneamino)phenols Ia and Ib at a ratio
Scheme 1.
HO
HCl
CHAr
N
Cl–
H
HO
I'a, I'b
CHAr
N
O
O
P(OEt)2
P(OEt)2
(EtO)2PCl, CHCl3
–HCl
HCl
Ia, Ib
ArCH
NH
ArCH
N
N
Cl–
H
IIa, IIb
IIIa, IIIb
Cl–
2'
3'
2
O
4'
11–14
EtO
O
1
O
NH 9
1'
Ar
Ar
10
EtO
Ar
P
EtO
Ar
P
*
3
IIIa, IIIb
*
*
8
*
P
OEt
P
OEt
–2EtCl
5
N
H
7
O
4
6
N
O
OEt
Cl–
O
H
IVa, IVb
Va, Vb
Ar = 4-MeOC6H4 (a), 4-BrC6H4 (b).
622

A CONVENIENT SYNTHESIS OF 2,7-DIOXA-5,10-DIAZA-3λ5,8λ5-DIPHOSPHA-...
623
Scheme 2.
(EtO)2PCl, CHCl3
pyridine
–C5H5N
C5H5N
III
I
II
+
C5H5N· HCl
III
IV
V
–2EtCl
phonium intermediates IV via intermolecular “head-to-
tail” nucleophilic attack by the phosphorus atom on
electrophilic carbon atoms of the iminium group. Inter-
mediates IV are then converted into final macrocycles
V as a result of dealkylation as in Arbuzov reaction.
chloroform and diethyl ether to isolate 0.35 g of solid
iminophenol hydrochloride I′a. The filtrate was evap-
orated under reduced pressure, the residue was treated
with anhydrous diethyl ether, and the resulting powder
was filtered off, washed with diethyl ether (2×10 ml),
and dried under reduced pressure. The product (1.6 g)
was recrystallized from butanol. A thick oily substance
separated from the butanol solution and was treated
with diethyl ether to obtain solid compound Va which
was stable on exposure to air. Yield 1.32 g (65%),
mp 125–129°C. IR spectrum, ν, cm–1: 3297 (NH);
1247, 1202 (P=O), 1032, 980 (P–O–C). 1H NMR spec-
trum (CDCl3), δ, ppm: 1.02 br.t, 1.12 m, 1.18 br.t,
The structure of macrocyclic compounds Va and
1
Vb was confirmed by the H, 13C, and 31P NMR, IR,
and mass spectra and elemental analyses. In the
1H NMR spectra of Va and Vb doublet signals from
two protons in the PCH fragments (2JHP = 23–24 Hz)
were observed in the expected region, at δ 4–5 ppm.
Taking into account the presence in molecules V of
four pairwise equivalent chiral centers, these doublets
are likely to correspond to five possible diastereoiso-
mers (three d,l and two nonequivalent meso forms). It
should also be taken into account that two nonequiv-
alent phosphorus atoms in some diastereoisomers may
3
1.27 t, 1.32 m (15H, CH3, JHH = 7.0 Hz); 3.74 br.s
(5H, OCH3, OCH2); 3.92 br.m, 4.09 br.m, 4.18 br.m
2
(6H, OCH2); 4.70 br.d (1H, PCH, JPH = 24.0 Hz),
2
4.73 br.d (1H, PCH, JPH = 23.4 Hz), 4.76 br.d (1H,
PCH, 2JPH = 23.7 Hz); 6.44 br.m, 6.50 br.m, 6.84 br.m,
7.34 br.m (16H, Harom). 13C NMR spectrum (CDCl3),
δC, ppm (multiplicity in the proton-decoupled spectrum
is given in parentheses): 16.25 q.m (d), 16.27 q.m (d),
2
be characterized by different coupling constants JPH;
therefore, different signals may be observed in the
31P–{1H} NMR spectra.
1
The reactions of diethyl phosphorochloridite with
iminophenols Ia and Ib in the presence of pyridine as
external base were not accompanied by formation of
hydrochlorides I′a and I′b (Scheme 2). In this case,
reactive imino phosphite hydrochlorides IIIa and IIIb
are formed via transfer of HCl from pyridine hydro-
chloride to initially generated imino phosphites IIa and
IIb. The occurrence of such equilibrium process is
indicated by the presence in the 31P–{1H} NMR spec-
tra of a weak downfield signal corresponding to struc-
ture IIIa or IIIb, δP 134.9 (IIa, IIb), 135.1 and
135.2 ppm (IIIa, IIIb). The reaction in the presence of
pyridine is characterized by appreciably higher yield of
Va and Vb, 78 and 70%, respectively, against 65 and
56% in the reaction with no base.
16.37 q.m (d), 16.46 q.m (d) (CH2CH3, JHC = 127.4–
3
2
127.5, JPC = 5.6–6.0, JHC = 3.0 Hz); 55.24 br.q (d)
1
(OCH3, JCH = 144.0 Hz); 55.33 br.d.d.m (br.d),
55.41 br.d.d.m (br.d), 55.57 br.d.d.m (br.d),
1
55.61 br.d.d.m (br.d), 55.80 br.d.d.m (br.d) (PC, JPC
=
1
152.7–153.5, JHC = 150–152 Hz); 62.59 br.t.m (br.d),
63.23 br.t.m (br.d), 63.29 br.t.m (br.d), 64.08 br.t.m
1
2
(br.d) (OCH2, JCH = 148.1–148.9, JPC = 5.7–6.9,
2JCH = 4.5 Hz); 114.12 br.d.m (br.s) (C13, JHC
=
1
160.5 Hz); 114.58 br.d.m (br.s) (C3′, JHC = 158.0 Hz);
1
121.24 br.d.m (br.s), 121.05 br.d.m (br.s) (C2′, JHC
=
1
160.9–161.2 Hz); 127.09 br.m (br.d) (C11, JPC = 8.5–
2
8.6 Hz); 129.13 br.d.m (d), 129.21 br.d.m (d) (C12,
1JHC = 160.0–161.0, JPC = 5.3 Hz); 142.29 m (d),
3
142.30 m (d), 142.45 m (d), 142.55 m (d) (C4′, 3JPC
=
10.5–11.0 Hz); 143.56 br.m (br.d), 143.71 br.m (br.d),
143.75 br.m (br.d) (C1′, 2JPC = 10.5–11.0 Hz); 159.42 m
(s), 159.46 m (s), 159.48 m (s) (C14). 31P NMR spec-
trum (CDCl3), δP, ppm: 19.9, 20.3, 23.2. Mass spec-
trum: m/z 639 [M + H]+. Found, %: C 59.97; H 5.91;
N 4.68; P 10.19. C32H36N2O8P2. Calculated, %:
C 60.19; H 5.64; N 4.39; P 9.72. M 638.59.
4,9-Bis(4-bromophenyl)-3,8-diethoxy-2,7-dioxa-
5,10-diaza-3λ5,8λ5-diphospha-1,6(1,4)-dibenzena-
cyclodecaphane-3,8-dione (Vb). A solution of 0.60 g
(3.83 mmol) of diethyl phosphorochloridite in 10 ml of
3,8-Diethoxy-4,9-bis(4-methoxyphenyl)-2,7-di-
oxa-5,10-diaza-3λ5,8λ5-diphospha-1,6(1,4)-diben-
zenacyclodecaphane-3,8-dione (Va). A solution of 1 g
(6.39 mmol) of diethyl phosphorochloridite in 15 ml of
anhydrous chloroform was added over a period of 1 h
under stirring at room temperature in an argon atmos-
phere to a suspension of 1.45 g (6.39 mmol) of
4-(4-methoxybenzylidene)aminophenol (Ia) in 70 ml
of anhydrous chloroform. The mixture was stirred for
1 h more and was kept for 11 days under argon. The
yellow precipitate was filtered off and washed with
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

DIMUKHAMETOV, MIRONOV
624
chloroform was added over a period of 1 h under
stirring at 20°C in a dry argon atmosphere to a suspen-
sion of 1.01 g (3.66 mmol) of 4-(4-bromobenzylidene-
amino)phenol (Ib) in 40 ml of anhydrous chloroform
containing 0.3 g (3.80 mmol) of freshly distilled pyri-
dine. The mixture was stirred for 1 h more and was
kept for 5 days. It was then filtered, the solvent was
distilled off from the filtrate under reduced pressure,
the residue was treated with anhydrous diethyl ether,
and the precipitate was filtered off, washed with di-
ethyl ether (2×10 ml), and recrystallized from butanol.
A thick oily substance separated from the butanol solu-
tion and was treated with diethyl ether to obtain off-
white solid compound Vb which was stable on ex-
posure to air. Yield 0.94 g (70%), mp 154–158°C. IR
spectrum, ν, cm–1: 3303 (NH); 1243, 1200 (P=O);
1034 (P–O–C). 1H NMR spectrum (CDCl3–acetone-d6,
1:1), δ, ppm: 1.01 br.m, 1.12 br.m, 1.22 br.m (6H,
162 MHz (31P). The IR spectra were recorded on
a Bruker Vector-22 instrument from thin films placed
between KBr plates. The Mass spectra were obtained
on a Dynamo MALDI TOF mass spectrometer
(Thermo Bioanalysis Finnigan, USA) equipped with
a pulse UV laser (λ 337 nm); nitroaniline was used as
matrix.
This study was performed under financial support
by the Ministry of Education and Science of the Rus-
sian Federation (Federal contract no. 02.740.11.0633).
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012