Heterocondensed 1,4-diphosphinines

Article abstract of DOI:10.1002/hc.1105

A reaction of phosphorus tribromide with a compound containing two 2,5-dimethyl-1-arylpyrrolyl-3 residues bound through a phosphorus atom gave rise to a new phosphorus-containing heterocyclic system, 1,4-diphosphinine. The new products thus obtained have been characterized and described.

Full text of DOI:10.1002/hc.1105

Heteroatom Chemistry
Volume 13, Number 1, 2002
Heterocondensed 1,4-Diphosphinines
Sergey P. Ivonin,1 Andrew A. Tolmachev,2 Alexander N. Chernega,2
and Alexander M. Pinchuk2
1Department of Chemistry, Dnepropetrovsk National University, per. Naychney 16,
Dnepropetrovsk-10, 49625, Ukraine
2Institute of Organic Chemistry, Ukrainian Academy of Sciences, Myrmanskaja str 5.
Kiev, 02094, Ukraine
Received 3 April 2001; revised 19 June 2001
ing two pyrrole residues by a phosphorus atom and
ABSTRACT: A reaction of phosphorus tribromide
cyclizing the molecule by treating it with phosphorus
with a compound containing two 2,5-dimethyl-1-
tribromide.
arylpyrrolyl-3 residues bound through a phosphorus
atom gave rise to a new phosphorus-containing het-
erocyclic system, 1,4-diphosphinine. The new products
thus obtained have been characterized and described.
RESULTS AND DISCUSSION
The dipyrrolylthioamide (1) was found to react
C
2002 John Wiley & Sons, Inc. Heteroatom Chem 13:46–
with phosphorus tribromide in pyridine to yield
1,4-diphosphinine (2), which has been identified by
its 31P NMR spectrum ( P = 35.0; 136.0 ppm) and
characterized by converting it into thioamide (3),
thioesters (4) and (5), and phosphinic acid (6).
The structures of compounds 3–6 were determi-
nant by 31P and 1H NMR spectroscopy (see Tables 1
and 2) and the composition was supported by ele-
mental analyses (see Table 1).
52, 2002; DOI 10.1002/hc.1105
INTRODUCTION
The synthetic access to C-phosphorylated five-
membered heterocycles via the electrophilic phos-
phorylation with P(III) halides in basic media
enables both one and two phosphorus-containing
substituents to be introduced in a heterocyclic
molecule [1–4]. Of particular preparative inter-
est are heterocycles for which the P-containing
substituents can be introduced at the neighbor-
ing carbon atoms. We believe heterocyclic sys-
tems of this kind will be promising in the
synthesis of heterocondensed 1,4-diphosphinines.
Here, this synthetic line is exemplified by the
use of 2,5-dimethyl-N-arylpyrroles as starting sys-
tems (previously we reported their mono and
bisphosphorylation [3]). Our synthetic strategy on
the pathway to 1,4-diphosphorines included bind-
The molecular structure of compound 3c was de-
termined by x-ray diffraction. The perspective view
of molecule 3c is shown in Fig. 1 [5], and the se-
lected geometrical parameters are given in Table 3.
The P(1)P(10)N(2)N(20)C(5–8)C(50–80) central tri-
cyclic system is planar: deviations from the least-
˚
squares plane do not exceed 0.019 A, the dihedral
angle between six- and five-membered cycles being
only 1.5 . The C(11–16) benzene ring is turned out
from this plane by 79.0 . Bond lengths and angles in
3c are unexceptional [6,7].
There is an another scheme for the synthe-
sis of 1,4-diphosphinine with the same substituents
at the phosphorus atom. At first, 2,5-dimethyl-
N-(p-tolyl)pyrrole (7) was reacted with phospho-
rus tribromide in pyridine in a 2:1 ratio to form
Correspondence to: Sergey P. Ivonin, Heroev Stalingrada 133/60,
Dnepropetrovsk, 49033, Ukraine; e-mail: ivonin@dp.ukrtel.net.
c
2002 John Wiley & Sons, Inc.
46

Heterocondensed 1,4-Diphosphinines 47
TABLE 1 Yields, Data of Elemental Analysis, and 31P NMR Spectroscopic Characteristics for Compounds 3–25
Found (%) Calcd. (%)
No.
Yield (%)
mp ( C)
P (CHCl3)
Formula
P
N
3
4
67
76
62
55
74
67
68
73
43
64
47
64
58
53
62
65
53
63
67
335
180
147
170
321
250
234
160
295
198
165
234
221
279
254
168
320
215
246
34.6
C34H42N4O2P2S2
C31H37N3O2P2S2
9.21 (9.32)
10.01 (10.16)
9.25 (9.22)
8.51 (8.43)
7.12 (6.89)
6.18 (6.25)
7.14 (7.46)
4.45 (4.76)
4.92 (5.05)
3.81 (4.13)
4.08 (3.92)
8.14 (7.95)
6.55 (6.89)
6.93 (6.71)
8.82 (8.58)
7.35 (7.44)
5.75 (6.06)
4.98 (5.32)
5.11 (4.77)
5.78 (5.67)
9.07 (8.86)
10.84 (10.73)
34.0; 56.0
5
34.8; 56.5
C36H39N3O2P2S2
6
9
34.8; 23.0d JHP = 280 Hz
C30 35
H
N3O2P2S2
10.54 (10.99)
10.18 (10.53)
10.91 (11.17)
8.87 (9.13)
39.1
C26 26
H Br2N2P2
10
11
12
13
14
15
16
17
18
20
22
23
24
25
55.7
C28H32N2O2P2S2
C38H36N2O2P2S2
54.8
55.1
C
38H34F2N2O2P2S2
8.74 (8.67)
20.1
C40 42
H
N4P2S2
F6N4P2S2
8.88 (8.79)
20.3
C40 36
H
7.34 (7.62)
21.0
C
38H36Br2N4P2S2
7.13 (7.42)
3.4
C36 38
H
N4P2S2
10.01 (9.49)
8.51 (8.23)
6.3
C44H42N4P2S2
47.0d JHP = 150 Hz
C26 28
H
H
N2O2P2
N2O2P2S2
13.64 (13.40)
11.42 (11.76)
10.84 (10.56)
12.37 (12.53)
9.71 (9.79)
2.9
C26 28
60.2;83.5
8.1
C29H36N2O3P2S2
C26 28
C34 42
H
N2O4P2
16.6
18.4
H N4O4P2
C
46H52N6O2P2
8.17 (7.91)
Values within parentheses represent the percentage.
bromophosphine (8), which, when treated with
phosphorus tribromide (1 equivalent), led to 1,4-
diphosphinine (9), isolated in an analytically pure
state and in high yield. It is a crystalline compound,
stable in the absence of atmospheric moisture, with
the structure confirmed by the 31P and 1H NMR
spectra (see Tables 1 and 2) and the composition sup-
ported by the elemental analyses (see Table 1).
Because of the accessibility of bisbromophos-
phine 9, it became possible to obtain thiophospho-
nates 10–12, thioamides 3, 13–15, phosphine thiox-
ides 16, 17, and bisphosphinous acid 18.
TABLE 2 1H NMR Data for Compounds 3–25 in CDCl3: , Multiplicity, J (Hz)
Tol
No m-Tol o-Tol JHH
Me-Tol Me-Het
Other Signals
3
4
7.10
7.11
7.34
7.35
7.8
8.1
2.46
2.40
2.40
2.40
2.57
2.46
2.43
2.43
2.50
2.50
2.45
2.38
2.40
2.40
2.40
2.20
2.41
2.21
2.25
2.34
2.34
2.35
3.2m (8H, CH2 N); 3.6m (8H, CH2 O)
3.2m (4H, CH2 N); 3.47d J HP = 11.0 (3H, Me O); 3.6m (4H, CH2 O)
3.2m (4H, CH2 N); 3.6m (4H, CH2 O); 7.3m (13H, Ar)
3.2m (4H, CH2 N); 3.6m (4H, CH2 O); 7.58d J HP = 280 (1H, H P)
5
6
9
7.11
7.05
7.12
6.95
6.93
7.35
7.30
7.34
7.04
7.06
8.1
8.0
8.0
8.0
8.2
10
11
12
13
14
15
3.50d J HP = 16.0 (6H, Me O)
7.2m (10H, Ph)
7.4m (8H, Ar)
7.3m (18H, Ar+ NH)
7.4m (18H, Ar+ NH)
7.4m (18H, Ar+ NH)
16
6.95
7.10
8.1
2.60
2.20
3.95s (6H, Me-Het); 6.13dd J HH = 3.0 J HP = 7.1 (1H; H3); 6.6m
(1H; H4); 6.9m (1H; H5)
3.27s (6H, Me-Het); 7.5m (18H, Ar+ Het)
7.37d J HP = 150 (1H, H P)
9.5sa (2H, OH)
17
18
20
22
2.58
2.46
2.40
2.35
2.44
2.46
2.46
2.44
2.20
2.26
2.33
1.98
2.12
2.34
2.33
2.33
7.11
7.31
6.98
7.35
7.55
7.59
8.1
8.5
8.2
3.22d J HP = 38 (3H, OMe); 3.58d J HP = 18 (6H, OMe); 6.33d J HP
=
5.6 (1H, H-Het)
23
24
25
7.11
7.09
7.36
7.35
7.35
8.1
8.1
7.8
8.5sa (2H, OH)
3.2m (8H, CH2 N); 3.6m (8H, CH2 O)
3.10m (16H, CH2 N); 6.50dd J HH = 8.1, J HH = 1.7 (2H, p-Ph); 6.75dd
J HH = 8.1, J HH = 1.7 (4H, o-Ph); 7.1m (8H, m-Tol + m-Ph)
aBroadened.

48 Ivonin et al.
FIGURE 1 Perspective view and labeling scheme for molecule 3c (hydrogen atoms are omitted for clarity). The primed atoms
are generated from the asymmetric unit using the inversion center.
The phosphorus atom in 1,4-diphosphinine (9)
was quite readily oxidized with elemental sulfur to
give the corresponding thiodibromophosphine (19);
if treated with water, the latter was converted into
bisthiophosphinic acid (20).
SCHEME 2
As an interesting finding, one C P bond is
cleaved under the action of excess methanol to form
phosphonate 21, which has been isolated, on oxidiz-
ing it with sulfur, in the form of thiophosphonate 22
(as evidenced by nonequivalent methyl groups, the
presence of an 3H proton).
By the Todd–Atherton reaction, bisphosphinous
acid 18 was used to obtain, with good yields, bispho-
sphinic acid 23 and bisaminophosphinates 24 and
SCHEME 1
25.

Heterocondensed 1,4-Diphosphinines 49
˚
TABLE 3 Selected Bond Lengths (A) and Angles (deg) in 3c
Bond lengths
S(1) P(1)
P(1) N(1)
P(1) C(5)
1.9474(9)
1.665(2)
1.779(2)
1.780(2)
1.377(3)
1.377(3)
1.439(3)
1.431(3)
1.375(3)
1.379(3)
P(1) C(6)
N(2) C(70)
N(2) C(8)
N(2) C(11)
C(5) C(60)
C(5) C(8)
C(6) C(7)
Bond angles
SCHEME 4
S(1) P(1) N(1)
S(1) P(1) C(5)
N(1) P(1) C(5)
S(1) P(1) C(6)
N(1) P(1) C(6)
C(5) P(1) C(6)
C(70) N(2) C(8)
P(1) C(5) C(60)
C(60) C(5) C(8)
P(1) C(6) C(50)
P(1) C(6) C(7)
N(20) C(7) C(6)
N(2) C(8) C(5)
111.14(8)
114.29(9)
104.22(11)
114.04(8)
108.87(11)
103.56(11)
110.3(2)
128.74(18)
108.1(2)
127.67(18)
125.41(19)
107.6(2)
107.0(2)
The primed atoms are generated from the asymmetric unit using the
inversion center.
EXPERIMENTAL
1H and 31P NMR spectra were run on a Varian-
VXR 300 spectrometer with TMS being used as an
SCHEME 5
1
internal standard for H signals, and 85% H3PO4 as
1
1
1.21 g cm , space group P21/c, = 18.95 cm ,
crystal size ca. 0.31 0.41 0.47 mm. All crystallo-
graphic measurements were performed at 18 C on
a CAD-4-Enraf-Nonius diffractometer operating in
the ω 2 scan mode (the ratio of the scanning rates
ω/2 = 1.2). Intensity data were collected within the
range 2 < < 65 (0 < h < 17, 0 < k < 19, 15 <
l < 15) using graphite monochromated Cu K radi-
an external standard for 31P signals. All manipula-
tions were carried out in anhydrous solvents.
X-ray Structure Determination of 3c
Crystal data: C34H42N4O2P2S2 3C6H6, M = 899.14 mo-
noclinic, a = 13.787(2), b= 16.011(2), c= 12.307
3
˚
˚
(2) A,
= 114.25(1) , V = 2476.9 A , Z = 2, d =
˚
ation ( = 1.54178 A). Intensities of 4585 reflections
(4217 unique reflection, R= 0.023) were measured.
Data were corrected for Lorentz and polarization ef-
fects and an empirical absorption correction based
on azimuthal scan data [8] was applied. The struc-
ture was solved by direct methods and refined by the
full-matrix least-squares technique in the anisotropic
approximation using the CRYSTALS program pack-
age [9]. In the refinement 3212 reflections with I >
3␴(I) were used. Most (ca. 80%) of the hydrogen
atoms were located in the different Fourier maps;
the remaining H atoms were placed in calculated
positions. All H atoms were included in the final re-
finement with fixed positional and thermal param-
eters. Convergence was obtained at R= 0.049 and
Rw = 0.053, GOF = 1.101 (280 refined parameters;
SCHEME 3

50 Ivonin et al.
˚
TABLE 4 Coordinates of Atoms and Equivalent Isotropic Thermal Parameters Beq (A) in 3c
Atom
x
y
z
Beq
S(1)
P (1)
O (1)
N (1)
N (2)
C (1)
C (2)
C (3)
C (4)
C (5)
C (6)
C (7)
C (8)
C (9)
C (10)
C (11)
C (12)
C (13)
C (14)
C (15)
C (16)
C (17)
C (18)
C (19)
C (20)
C (21)
C (22)
C (23)
C (24)
C (25)
C (26)
0.50629 (6)
0.54755 (5)
0.79268 (19)
0.63752 (16)
0.30433 (16)
0.7112 (3)
0.7445 (3)
0.7204 (3)
0.6843 (2)
0.44181 (18)
0.59738 (19)
0.68290 (19)
0.38018 (19)
0.7526 (2)
0.3849 (2)
0.22318 (19)
0.2476 (2)
0.1695 (3)
0.0675 (2)
0.0453 (2)
0.1224 (2)
0.0159 (3)
1.2220 (4)
1.2032 (5)
1.1030 (5)
1.0211 (5)
1.0379 (5)
1.1397 (6)
0.5075 (3)
0.4906 (3)
0.5169 (3)
0.17690 (5)
0.10322 (4)
0.21839 (17)
0.14847 (13)
0.09208 (13)
0.2121 (2)
0.2658 (2)
0.1579 (2)
0.0994 (2)
0.07647 (15)
0.00460 (15)
0.00732 (16)
0.13501 (16)
0.05349 (19)
0.22774 (17)
0.13106 (16)
0.1621 (3)
0.2016 (3)
0.2093 (2)
0.1778 (3)
0.1392 (2)
0.2530 (3)
0.0599 (3)
0.0100 (4)
0.0036 (4)
0.0309 (5)
0.0796 (5)
0.0945 (4)
0.0190 (3)
0.0812 (2)
0.0619 (3)
0.65882 (6)
0.55918 (5)
0.4543 (2)
0.52056 (18)
0.24727 (18)
0.5934 (3)
0.5152 (4)
0.3818 (3)
0.4537 (3)
0.4209 (2)
0.6253 (2)
0.7331 (2)
0.3405 (2)
0.8236 (2)
0.3438 (2)
0.1449 (2)
0.0556 (3)
0.0405 (3)
0.0499 (2)
0.0398 (3)
0.1372 (3)
0.1554 (3)
0.7278 (6)
0.8066 (5)
0.7947 (5)
0.7042 (7)
0.6246 (7)
0.6367 (6)
0.8957 (3)
0.9620 (4)
0.9332 (3)
0.0524
0.0327
0.0797
0.0386
0.0382
0.0602
0.0751
0.0740
0.0556
0.0342
0.0345
0.0383
0.0378
0.0551
0.0489
0.0396
0.0692
0.0770
0.0523
0.0720
0.0660
0.0776
0.1146
0.1209
0.1293
0.1403
0.1556
0.1423
0.0735
0.0763
0.0726
The C(18)–C(24) atoms belong to the solvate benzene molecules.
obs./variabl. 11.5; the largest and minimal peaks in
mixture and then it was kept at 60 C for 4 h. The
solvent was evaporated under vacuum, and the
resulting residue was boiled with water (100 ml),
filtered off, and crystallized from ethanol.
3
˚
the final difference map, 0.30 and 0.37 e/A ). The
Chebushev weighting scheme [10] with parameters
1.46, 0.29, 0.72, 0.40, and 0.10 was used. The final
atomic coordinates are listed in Table 4.
Full crystallographic details have been deposited
at the Cambridge Crystallographic Data Centre
(CCDC). Any request to the CCDC for these materials
should quote the full literature citation and reference
number CCDC 158332.
Pyrrolo[30,40:5,6][1,4]diphosphorino[2,3-c]pyr-
role-2,4,6,8-tetrahydro-4-methoxy-1,3,5,7-tetrame-
thyl-2, 6-bis(4-methylphenyl)-8-(4-morpholinyl)-4,
8-disulfide (4). To a stirred solution of dipyrrolylth-
ioamide 1 (0.01 mol) in pyridine (30 ml), a solution
of phosphorus tribromide (0.01 mol) was added
dropwise over 5 min; 24 h later ( P = 35.0; 136.0
ppm), a solution of methanol (0.02 mol) and triethyl-
amine (0.03 mol) in benzene (50 ml) was added drop-
wise to the stirred reaction mixture over 20 min and
sulfur (0.01 mol) was then poured into it. After
having been allowed to stand at 60 C for 4 h, the
mixture was evaporated under vacuum. The result-
ing residue was boiled with water (100 ml), filtered
off, and crystallized from the mixture ethanol:water
(1:1).
Pyrrolo[30,40:5,6][1,4]diphosphorino[2,3-c]pyr-
role-2,4,6,8-tetrahydro-1,3,5,7-tetramethyl-2,6-bis
(4-methylphenyl)-4,8-di(4-morpholinyl)-4,8-disulfide
(3). To a stirred solution of dipyrrolylthioamide
1 [3] (0.01 mol) in pyridine (30 ml), a solution of
phosphorus tribromide (0.01 mol) was added drop-
wise over 5 min; 24 h later ( P = 35.0; 136.0 ppm),
a solution of morpholine (0.02 mol) and triethyl-
amine (0.03 mol) in benzene (100 ml) was added
dropwise to the stirred reaction mixture over 20 min.
After 5 h, sulfur (0.01 mol) was poured into the

Heterocondensed 1,4-Diphosphinines 51
Pyrrolo[30,40:5,6][1,4]diphosphorino[2,3-c]pyr-
role-2, 4, 6,8-tetrahydro-1,3,5,7-tetramethyl-2,6-bis
(4-methylphenyl)-4-(4-morpholinyl)-8-phenoxy-4,8-
disulfide (5). To a stirred solution of dipyrrolylthio-
amide 1 (0.01 mol) in pyridine (30 ml), a solution of
phosphorus tribromide (0.01 mol) was added drop-
wise over 5 min; 24 h later ( P = 35.0; 136.0 ppm),
a solution of phenol (0.01 mol) and triethylamine
(0.03 mol) in benzene (50 ml) was added dropwise to
the stirred reaction mixture over 20 min and sulfur
(0.01 mol) was then poured into it. After having been
allowed to stand at 80 C for 6 h, the mixture was
evaporated under vacuum. The resulting residue
was boiled with water (100 ml), filtered off, and
crystallized from the mixture ethanol:water (1:2).
(20 ml) was added dropwise to the stirred reaction
mixture. After the mixture had been held at 60 C for
5 h, it was evaporated under vacuum. The resulting
residue was boiled with water (100 ml), and the pre-
cipitate was filtered off. The product was crystallized
from ethanol.
General Procedure for Preparation
of Thioamidophosphonites 13–15
To a solution of bisbromophosphine 9 (0.01 mol) in
pyridine (50 ml), sulfur (0.02 mol) was added and
then a solution of aniline (0.02 mol) and triethyl-
amine (0.02 mol) in pyridine (20 ml) was added drop-
wise to the stirred reaction mixture. After the mixture
had been held at 60 C for 5 h, it was evaporated under
vacuum. The resulting residue was boiled with water
(100 ml), and ethanol (50 ml) and the precipitate was
filtered off.
Pyrrolo[30,40:5,6][1,4]diphosphorino[2,3-c]pyr-
role-2,4,6,8,8,8-hexahydro-1,3,5,7-tetramethyl-2,6-
bis (4-methylphenyl)-4-(4-morpholinyl)-8-oxo-, 4-sul-
fide (6). To a stirred solution of dipyrrolylthioamide
1 (0.01 mol) in pyridine (30 ml), a solution of phos-
phorus tribromide (0.01 mol) was added dropwise
over 5 min; 24 h later ( P = 35.0; 136.0 ppm), the
reaction mixture was evaporated under vacuum
and the residue was dissolved in methylene chloride
(100 ml). On filtration of the mixture, water (20 ml)
was poured into the filtrate. After 24 h, the organic
layer was separated, washed with water (20 ml),
dried with sodium sulfate, and evaporated under
vacuum. The product was purified by precipitating
it from ethanol by addition of water.
General Procedure for Preparation
of Thioxides 16, 17
To a stirred solution of bisbromophosphine 9
(0.01 mol) in pyridine (50 ml), a solution of hetero-
cycle (0.2 mol) and triethylamine (0.02 mol) in pyri-
dine (20 ml) was added dropwise; 72 h later, sulfur
(0.02 mol) was added to the reaction mixture and it
was allowed to stand at 60 C for 5 h. After filtration,
the filtrate was evaporated under vacuum. The re-
sulting residue was boiled with water (100 ml), and
the precipitate was filtered off. The product was crys-
tallized from ethanol.
Pyrrolo[30,40:5,6][1,4]diphosphorino[2,3-c]pyr-
role,14,8-dibromo-2,4,6,8-tetrahydro-1,3,5,7-tetrame-
thyl-2,6-bis(4-methylphenyl) (9). To a stirred solu-
tion of pyrrole (0.01 mol) in pyridine (50 ml), a
solution of phosphorus tribromide (0.005 mol) in
pyridine (10 ml) was added dropwise over 5 min;
2 h later, the same portion of a pyridinec solu-
tion of phosphorus tribromide was added to the
reaction mixture in the same manner. After 72 h
( P = 136.0 ppm), the mixture was filtered and the
filtrate was evaporated under vacuum. The residue
was dissolved in benzene (100 ml), filtered off, and
the filtrate was evaporated under vacuum. The
product was crystallized from the mixture benzene:
heptane (1:1).
Pyrrolo[30,40:5,6][1,4]diphosphorino[2,3-c]pyr-
role-2,4,4,4,6,8,8,8-octahydro-1,3,5,7-tetramethyl-2,
6-bis(4-methylphenyl)-4,8-dioxide (18). To a solu-
tion of bisbromophosphine 9 (0.01 mol) in methy-
lene chloride (100 ml), water (20 ml) was added.
After 24 h, the organic layer was separated, washed
with water (20 ml), dried with sodium sulfate, and
evaporated under vacuum to afford the residue
which was boiled with ether (20 ml).
Pyrrolo[30,40:5,6][1,4]diphosphorino[2,3-c]pyr-
role,2,4,6,8-tetrahydro-4,8-dihydroxy-1,3,5,7-tetrame-
thyl-2,6-bis(4-methylphenyl)-,4,8-disulfide (20). To
a solution of bisbromophosphine 9 (0.01 mol) in
benzene (100 ml), sulfur (0.02 mol) was added and
the mixture was boiled for 10 h. On evaporation
under vacuum, the resulting residue was boiled first
with water (100 ml) and then with ether (50 ml).
General Procedure for Preparation
of Thiophosphonites 10–12
To a solution of bisbromophosphine 9 (0.01 mol) in
pyridine (50 ml), sulfur (0.02 mol) was added, and
then a solution of the corresponding alcohol ROH
(0.02 mol) and triethylamine (0.02 mol) in pyridine
Phosphonothioic acid [4-[[2,5-dimethyl-1-(4-meth-
ylphenyl)-1H-pyrrol-3-yl]methoxyphosphinothioyl]-
2,5-dimethyl-1-(4-methylphenyl)-1H-pyrrol-3-yl]

52 Ivonin et al.
O,O-dimethyl ester (22). To a solution of bisbro-
mophosphine 9 (0.01 mol) in pyridine (50 ml),
methanol (0.1 mol) was added and the reaction
mixture was kept at 50 C for 10 h. After filtration,
the filtrate was evaporated under vacuum and the
resulting residue was boiled with water (100 ml).
The product was purified by precipitation from
ethanol by addition of water.
of the solvent under vacuum, the resulting residue
was boiled successively with water (50 ml) and ether
(50 ml).
REFERENCES
[1] Ivonin, S. P.; Terikovskaya, T. E.; Chaikovskaya, A.
A.; Marchenko, A. P.; Koydan, G. N.; Pinchuk, A. M.;
Tolmachev, A. A. Heteroat Chem 1999, 10, 213–221.
[2] Ivonin, S. P.; Anishchenko, A. A.; Kurochkin, A.
F.; Tolmachev, A. A. Heteroat Chem 1998, 9,
559–563.
[3] Tolmachev, A. A.; Ivonin, S. P.; Chaikovskaya, A. A.;
Terikovskaya, T. E.; Pinchuk, A. M. Heteroat Chem
1999, 10, 223–230.
[4] Keglevich, G.; Cuiuunbaatar, T.; Dobo, A.; Toke, L. J
Chem Soc Perkin Trans 2000, 1, 1495.
[5] Watkin, D. J.; Prout, C. K.; Pearce, L. J. Cameron;
Chemical Crystallography Laboratory, University of
Oxford: Oxford, 1996.
[6] Naumov, V. A.; Vilkov, L. V. Molecular Structures
of Organophosphorus Compounds, Nauka, Moscow,
1986.
[7] Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer,
L.; Orpen, A. G.; Taylor, R. J. Chem Soc Perkin Trans
1987, 2, P1.
Pyrrolo[30,40:5,6][1,4]diphosphorino[2,3-c]pyr-
role-2, 4, 6, 8-tetrahydro-4, 8-dihydroxy-1,3,5,7-tetra-
methyl-2,6-bis(4-methylphenyl)-4,8-dioxide (23). To
a solution of bisbromophosphine 18 (0.01 mol)
in benzene (100 ml), triethylamine (0.02 mol) and
carbon tetrachloride (0.02 mol) were added, and the
reaction mixture was boiled for 5 h. After addition
of water (5 ml), it was boiled for another 3 h. The
solvent was evaporated under vacuum to provide the
residue which was boiled successively with water
(20 ml) and ether (30 ml).
General Procedure for Preparation
of Amidophosphonites 24, 25
[8] North, A. C. T.; Phillips, D. C.; Mathews, F. S. Acta
Crystallogr 1968, A24, 351.
[9] Watkin, D. J.; Prout, C. K.; Carruthers, J. R.;
Betteridge, P. W. Crystals, issue 10; Chemical Crys-
tallography Laboratory, University of Oxford: Oxford,
1996.
[10] Carrythers, J. R.; Watkin, D. J. Acta Crystallogr 1979,
A35, 698.
To a solution of bisbromophosphine 18 (0.01 mol)
in benzene (100 ml), triethylamine (0.04 mol), car-
bon tetrachloride (0.02 mol), and the corresponding
amine (0.02 mol) were added, followed by boiling
of the reaction mixture for 15 h. After evaporation