Synthesis of bis- and Tris(3-H-1,3-azaphospholo)benzenes

Article abstract of DOI:10.1002/hc.21125

The previously developed intramolecular cyclocondensation of C-phosphanyl(N-aryl)formamidines into 3-H-1,3-benzazaphospholes has been successfully extended to 1,3-diaminobenzene and 1,3,5-triaminobenzene. Its condensation presents the way to tricyclic and

Full text of DOI:10.1002/hc.21125

Heteroatom Chemistry
Volume 25, Number 1, 2014
Synthesis of Bis- and
Tris(3-H-1,3-azaphospholo)benzenes
Anatoliy Marchenko, Heorgiy Koidan, Anastasiya Huryeva,
Radomyr Smaliy, Yurii Vlasenko, Oleksii Gutov,
and Aleksandr Kostyuk
Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanska Street 5,
Kyiv-94, 02094, Ukraine
Received 30 July 2013; revised 6 September 2013
compounds have been the subject of a few stud-
ABSTRACT: The previously developed intramolec-
ies concerning their synthesis methods, structural
ular cyclocondensation of C-phosphanyl(N-aryl)
features, and metal coordination properties [1, 2].
formamidines into 3-H-1,3-benzazaphospholes has
It should be noted that 1,3-azaphosphole can ex-
been successfully extended to 1,3-diaminobenzene and
ist in two tautomeric forms, with either a σ2,λ3-
1,3,5-triaminobenzene. Its condensation presents the
phosphorus (I) or a σ3,λ3-phosphorus (II) (Fig. 1).
way to tricyclic and tetracyclic azaphospholes. Their
3H-Azaphospholes lack the conjugation be-
structures were confirmed by spectroscopic methods
tween the phosphorus lone pair and the rest of
and key tricyclic and tetracyclic compounds were fur-
the π system because of the pyramidal structure
ther characterized by single crystal X-ray diffraction.
of σ3,λ3-phosphorus [5]. A general synthetic ap-
ꢀC
2013 Wiley Periodicals, Inc. Heteroatom Chem.
proach to 3H-1,3-benzazaphospholes has only re-
cently been reported. The starting C-phosphanyl(N-
aryl)formamidines prepared using a diverse set of
anilines have been shown to undergo cyclization
yielding 3H-1,3-benzazaphospholes. The rate of the
cyclization has been shown to depend on the ben-
zene ring substituent electron-donating efficiency.
At the same time, the method tolerates various sub-
stituents [6]. In this contribution, we describe the
extension of the method to 1,3-diaminobenzene and
1,3,5-triaminobenzene to prepare polycyclic 3H-1,3-
benzazaphospholes.
25:1–9, 2014; View this article online at wileyon-
linelibrary.com. DOI 10.1002/hc.21125
INTRODUCTION
Presently, the number of synthetic routes to phos-
phorus heterocycles is considerably limited com-
pared with the multitude of methods for the prepa-
ration of their oxygen and nitrogen analogues.
Among phosphorus heterocycles, fused azaphosp-
holes are of considerable interest [1, 2]. Poly(3-H-1,
3-azaphospholo)benzenes are supposed to be highly
symmetrical compounds that might be useful start-
ing materials for metal-organic frameworks [3] and
symmetrical tripod scaffold for the construction of
receptors [4]. Azaphospholes and related annulated
RESULTS AND DISCUSSION
First, we have investigated the reaction with
1,3-diaminobenzene. Unlike 1,2-diaminobenzene,
1,3-diaminobenzene was readily phosphory-
lated with a twofold amount of N,N-dimethyl-P-
(trichloromethyl)phosphonamidous chloride at
both amino groups affording trivalent derivative.
It was not isolated as an individual compound,
Correspondence to: Aleksandr Kostyuk; e-mail: a.kostyuk@
yahoo.com.
ꢀC
2013 Wiley Periodicals, Inc.
1

2
Marchenko et al.
R
P
R
N
P
N
P(NMe2)2
NMe2
P
N
N
N
II
I
N
5
4
3H -1,3-Azaphosphole
1H -1,3-Azaphosphole
SCHEME 2 Synthesis of substituted benzazaphospholes 5.
FIGURE 1 Tautomeric forms of azaphospholes.
The reaction of compound 3 with two equiv-
alents of hexamethylphosphorus triamide was
monitored by 31P NMR spectroscopy at room tem-
perature. 31P NMR spectra indicated a gradual disap-
pearance of hexamethylphosphorus triamide (δp 123
ppm) and the appearance of tris(dimethylamino)
phosphane selenide (δp 84 ppm) and compound 7
(δp 95 and 59 ppm) (Scheme 3). In a month, the reac-
tion came to completion. The solvents were carefully
evaporated keeping temperature below 20◦C.
We have isolated compound 7 in a mix-
ture with tris(dimethylamino)-phosphane selenide.
It was characterized by 31P, 1H, and 13C NMR
spectroscopy. In 13C NMR spectrum, compound 7
showed resonance typical for the formamidine car-
bon at 161.8 (d, J = 30 Hz) ppm and for the benza-
zaphosphole carbon at 176.5 (d, J = 23 Hz) ppm.
Heating this mixture led to compounds 8 and 9
(Scheme 4). Compound 6 was not registered by
31P NMR spectroscopy. Therefore, one can draw a
conclusion that electron-donating capability of the
N C(NMe2)P(NMe2)2 group is equal or greater of
that of NMe2.
Thus, the reduction of compound 3 easily pro-
ceeds at room temperature, but slight heating is
sufficient to complete the second cyclization step
(Scheme 4). The intermediate 7 has two possibili-
ties for the cyclization: into linear 8 or angular 9.
As trivalent phosphorus derivatives are labile com-
pounds, they were oxidized into penatavalent deriva-
tives 10 and 11 and separated by chromatography
as mixtures of diastereomers. The first fraction (Rf
0.03–0.15) was compound 10, and two other frac-
tions (Rf 0.3–0.4 and 0.5–0.7) were proved to be
but it was characterized by 31P nuclear magnetic
resonance (NMR) spectroscopy (δp 80 ppm). Then
the compound was oxidized with selenium to the
pentavalent derivative 2 as a mixture of diastere-
omers. Although the mixture was separated by
chromatography into individual diastereomers,
their absolute configurations were not assigned.
Upon treatment with an excess of dimethylamine at
room temperature in a sealed vial, the mixture of
diastereomers 2 was converted into a stable crys-
talline pentavalent C-phosphorylated formamidine
3 in high yield (Scheme 1).
In our previous work, we showed that the
cyclization of C-phosphorylated N,N-dimethyl-Nꢁ-
arylformamidines critically depends on the posi-
tion and electron-donating capability of substituents
at the aryl ring (Scheme 2). The cyclization pro-
ceeds with the elimination of dimethylamine and its
mechanism was described in detail [6b]. Electron-
donating substituents at the meta position promoted
cyclization the best. For R = Me2N, compound 4 was
not isolated as it spontaneously underwent cycliza-
tion to give benzazaphosphole 5 (Scheme 2). The
compounds 4 bearing less electron-donating sub-
stituents are rather stable.
It was expected that the reduction of pentava-
lent compound 3 with two equivalents of hexam-
ethylphosphorus triamide would afford trivalent
C-phosphorylated formamidine 6. As electron-donor
properties of N C(NMe2)P(NMe2)2 group were not
described in the literature, it was difficult to estimate
the rate of the cyclization and whether it would be
stable or not.
NHP(CCl3)NMe2
NH2
1.
NMe2
CCl3(NMe2)PCl,
Et3N
Se
10 Me2NH
Me2N
(NMe )
N
N
P
2 2
Se
NHP(CCl3)NMe2
Se
NH2
2.
Se
(NMe )
P
2 2
2
1
3
Se
SCHEME 1 Synthesis of P(V) formamidine 3.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of Bis- and Tris(3-H-1,3-azaphospholo)benzenes
3
P(NMe2)2
Me2N
Me2N
(Me2N)2P
N
N
N
P
2 (Me2N)3P
NMe2
3
NMe2
−2 (Me2N)3PSe
NMe2
N
7
P(NMe2)2
6
SCHEME 3 Preparation of the intermediate compound 7.
NMe2
NMe2
Me2N
NMe2
NMe2
Me2N
P
N
N
2 (Me2N)3P
P
P
3
NMe2
Me2N
+
P
−2 (Me2N)3PSe
N
N
9
8
NMe2
Se
NMe2
P
Me2N
Se
Se
Me2N
Se
NMe2
P
N
P
NMe2
+
Me2N
N
P
Se
N
N
NMe2
10
11
SCHEME 4 Synthesis of compounds 10 and 11.
1
compound 11. Both in H and 13C spectra, charac-
teristic features of compound 10 are triplets coupled
to phosphorus atoms. Compound 11 lacks such sym-
metry (Fig. 2).
Furthermore, we have investigated the anal-
ogous transformation of 1,3,5-triaminobenzene.
We have started with the synthesis of compound
14 that was prepared by reacting 1,3,5-triamino-
benzene with N,N-dimethyl-P-(trichloromethyl)
phosphonamidous chloride (Scheme 6). Compound
14 was characterized by 31P NMR and further
transformed into selenide 15 possessing three chiral
phosphorus atoms. Compound 15 as the mixture
of diastereomers was treated with an excess of
dimethylamine to give a high melting compound
16. Pentavalent C-phosphorylated formamidine 16
was reduced with hexamethylphosphorus triamide
in 5 min at room temperature, but the intermediate
trivalent C-phosphorylated amidine was not regis-
tered as it immediately cyclized into azaphosphole
17. The latter was readily oxidized to pentavalent
As we failed to grow a single crystal of compound
10, it was reduced to trivalent derivative 6 and con-
verted into sulfur analog 12, which was studied by
the single crystal X-Ray analysis (Scheme 5).
The perspective view of 12 is given in Fig. 3.
The central tricyclic system C(1–8)P(1)P(2)N(1)N(2)
is almost planar (the maximum deviation from the
˚
least-square plane is 0.050 A). The terminal N(3),
N(4), and N(5) atoms have a trigonal-planar bond
configuration (corresponding sum of the bond an-
gles is 359.9(9)³, 360.0(1)³, and 357.0(9)³), and the
N(6) atom has a pyramidal bond configuration (sum
of the bond angles is 352.2(9)³).
Heteroatom Chemistry DOI 10.1002/hc

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Marchenko et al.
127.68 (t, JPC = 16.3)
7.32 (t, JPH = 9.6)
Se
NMe2
Se
N
Me2N
NMe2
NMe2
H
P
N
Se
NMe2
Me2N
P
P
P
NMe2
Me2N
114.28 (d, JPC = 3.8)
Se
N
N
Rf 0.3-0.4
11
133.73 (d, JPC = 13.8)
H
10
H
H
6.76 (t, JPH = 3.2)
6.68–6.58 m
112.19 (t, JPC = 5.6)
7.25 (dd, JPH = 9, JHH = 9)
FIGURE 2 Characteristic NMR data for compounds 10 and 11.
NMe2
S
Me2N
S
2 (Me N) P
1.
P
P
2
3
NMe2
N
10
Me2N
2. S
N
12
SCHEME 5 Synthesis of compound 12.
derivatives 18a–c. The molecular structure of 18b
was confirmed by single-crystal X-ray diffraction
(Fig. 4).
respectively. Interestingly, the double and the
triple intramolecular cyclocondensations proceed
more efficiently than formerly reported reac-
tion involving monoaminobenzene derivatives
[6]. Therefore, a facile synthetic route to 1,3-
azaphospholes starting from 1,3-diaminobenzene
and 1,3,5-triaminobenzene was developed.
The perspective view of the molecule 18b is given
in the Fig. 4. The molecule of 18b has three chi-
ral tetrahedral phosphorus atoms and crystallizes in
a chiral space group (P212121). The five-membered
heterocycles, which are adjacent to the central
C(1–6) cycle, are not planar and have an envelope
conformation: atoms C(5)C(4)N(4)C(9) are planar
EXPERIMENTAL
General
˚
within 0.002 A, and the “corner” C(5)P(3)C(9) forms
with this plane the dihedral angle of 4.61◦; the dihe-
dral angle between C(3)C(2)N(1)C(8) (planar within
All procedures with air and moisture sensitive com-
pounds were performed under an atmosphere of
dry argon in flame-dried glassware. Solvents were
purified and dried by standard methods. Melting
points (mp) were determined with an electrother-
mal capillary melting point apparatus and were un-
corrected. 1H spectra were recorded on a Bruker
Avance DRX 500 (500.13 MHz) or Varian VXR-300
(299.94 MHz) spectrometer. 13C NMR spectra were
recorded on a Bruker Avance DRX 500 (125.75 MHz)
spectrometer. 31P NMR spectra were recorded on a
Varian VXR-300 (121.42 MHz) spectrometer. Chem-
ical shifts (δ) are reported in ppm downfield relative
◦
˚
0.003 A) and C(3)P(2)C(8) is 8.61 ; the dihedral angle
˚
between C(1)C(6)N(7)C(7) (planar within 0.015 A)
and C(1)P(1)C(7) is 3.36◦. The N(2), N(5), N(6),
and N(8) atoms have a trigonal-planar bond con-
figuration (corresponding sum of the bond angles
is 360.0◦, 359.9◦, 357.5◦, and 360.0◦), and the N(3)
and N(9) atoms have a pyramidal bond configura-
tion (sum of the bond angles is 352.8◦ and 349.9◦,
correspondingly).
CONCLUSIONS
1
to internal tetramethylsilane (TMS) (for H and 13C
C-phosphanyl(N-aryl)formamidines derived from
1,3-diaminobenzene and 1,3,5-triaminobenzene
undergo intramolecular cyclocondensations fur-
nishing tricyclic and tetracyclic azaphospholes,
spectra) and external 85% H3PO4 (for 31P spectra).
Chromatography was performed on silica gel Geru-
dan SI60. Elemental analyses were performed at the
microanalytical laboratory of the Institute of the
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of Bis- and Tris(3-H-1,3-azaphospholo)benzenes
5
CCl3
NMe2
P
NH2
CCl3P(NMe2)Cl
Et3N
H
N
CCl3
NH
Se
Py
P
NMe2
Py/ C6H6
H2N
NH2
14
HN
CCl3
13
P
NMe2
Se
P
Se
Se
P
CCl3
NMe2
Me2N
Me2N
NMe2
NMe2
P
N
N
H
N
Se
P
CCl3
NH
Me2NH
NMe2
NMe2
(Me N) P
NMe2
3
2
3
Me2N
Se
N
Se
(Me N) PSe
-3
HN
CCl3
2
3
P
P
16
15
Me2N
NMe2
NMe2
Me2N
N
X
P
Me2N
NMe2
NMe2
N
P
N
N
P
N
P
X
NMe2
NMe2
P
X
Me2N
Me2N
P
NMe2
NMe2
N
X
Me2N
X = O (a), S (b)
Me2N
17
18a,b
SCHEME 6 Synthesis of compound 18.
Organic Chemistry National Academy of Sciences
of Ukraine.
cated in the difference Fourier maps and refined
with fixed positional and thermal parameters. The
absolute configuration was determined by the Flack
method [12]. Enantiopole parameters are 0.01(1)
(2557 Friedel pairs) for 18b and 0.04(7) (1989 Friedel
pairs) for 12.
Full crystallographic details have been deposited
at Cambridge Crystallographic Data Centre (CCDC)
(Table 1).
EXPERIMENTAL
All crystallographic measurements were performed
at 173 K on a Bruker Smart Apex II diffractome-
ter (MoKα). Data were corrected for Lorentz and
polarization effects. The SADABS procedure [7] ab-
sorption correction was applied. The structures were
solved by direct methods and refined by the full-
matrix least-squares technique in the anisotropic ap-
proximation using the SHELXS97 and SHELXL97
programs [8, 9] and CRYSTALS program package
[10]. In the refinement, the Chebychev weighting
scheme [11] was used. All hydrogen atoms were lo-
Nꢁ,Nꢁꢁ-1,3-Phenylenebis[1,1-bis(dimethylamino)-
N,N-dimethylphosphinecarboximidamide] Diselenide
2. 1,3-diaminobenzene (760 mg, 7 mmol) and
triethylamine (2.7 mL) in pyridine (20 mL)
were added to N,N-dimethyl-P-(trichloromethyl)
phosphonamidous chloride (3.2 g, 14 mmol) at
Heteroatom Chemistry DOI 10.1002/hc

6
Marchenko et al.
C10
S1
P1
C16
S2
N5
N6
C5
C7
P2
C9
C8
C2
C6
C4
C15
C11
C14
N4
C1
N3
N1
N2
C3
C12
C13
◦
˚
FIGURE 3 X-ray molecular structure for 12. Selected bond lengths [A] and angles [ ]: S(1)-P(1) 1.940(1), S(2)-P(2)
1.947(1), P(1)-N(5) 1.652(3), P(1)-C(1) 1.871(4), P(1)-C(8) 1.793(4), P(2)-N(6) 1.664(3), P(2)-C(5) 1.872(4), P(2)-C(6) 1.781(4);
C(1)P(1)C(8) 87.5(2), C(5)P(2)C(6) 88.9(2), C(1)N(1)C(2) 110.5(3), and C(4)N(2)C(5) 111.4(3).
C15
Rf 0.15–0.20 (eluent—ethyl acetate: hexane 1:5),
C17
S2
(1.02 g, 32%), mp 97–100◦С. 31P (CDCl3): δ 70.3.
N3
1Н (CDCl3, 300 MHz): δ 7.24 (t, 1H, J 7.8 Hz, HAr),
6.97 (m, 1H, HAr), 6.81 (dd, 2H, J1 2.1 Hz, J2 8.1 Hz,
N2
P2
C14
HAr), 5.21 (d, 2H, J 11.4 Hz, NH), 3.09 (d, 12H, J
C16
C4
C8
C18
N5
10.8 Hz, NCH3). 13С (CDCl3): δ 139.7, 130.3, 114.85
(d, J 6 Hz), 111.2 (t, J 4 Hz), 98.8 (d, J 65 Hz, CCl3),
39.9 (d, J 4 Hz).
N4
C3
N1
C9
C2
C1
Rf 0.4–0.45 (ethylacetate: hexane 1:5); (1.45 g,
1
45%), mp 176–178◦С. Н (CDCl3, 500 MHz): δ 7.27
C13
C12
C19
(m, 1H, HAr), 7.19 (t, 1H, J 8.0 Hz, HAr), 6.57 (dd,
2H, J1 2.0 Hz, J2 8.0 Hz, HAr), 5.14 (d, 2H, J 5.75 Hz,
NH), 3.17 (d, 12H, J 11.0 Hz, NCH3). 13С (CDCl3): δ
139.6, 130.3, 113.5 (d, J 10.0 Hz), 107.0 (m), 98.5 (d,
J 65 Hz, CCl3), 39.8 (d, J 5 Hz). 31P (CDCl3): δ 68.8.
P1
P3
C5
C20
C6
N9
S1
S3
N6
N7
C7
C21
N8
Nꢁ,Nꢁꢁ-1,3-Phenylenebis[1,1-bis(dimethylamino)-
N,N-dimethyl-phosphine-carboximidamide] Disele-
nide 3. A 10-mL vial was charged with a mixture
of isomers 2 (1.0 g, 1.5 mmol) and dimethylamine
(5 mL). The vial was sealed and the solution was
stirred at 25◦С for 24 h. An excess dimethylamine
was removed; the solid residue was washed with
degassed water (2 × 3 mL). The solid was dried
and recrystallized from diethyl ether (14 mL) and
left at –6◦С. The precipitated crystals were collected
and dried to give the target crystalline product 3
(860 mg, 91%); mp 156–157◦С.
C11
C10
FIGURE 4 Molecular structure for 18b.
–10◦С. The reaction mixture was stirred at room
temperature for 15 h. Selenium (1.5 g, 19 mmol)
was added, and the reaction mixture was stirred
at 25◦С for 30 h. The pyridine was evaporated
under reduced pressure. Acetonitrile (25 mL) was
added to the residue, the solution was refined
with charcoal, which was then filtered off, and
the filtrate evaporated. The residue was extracted
with boiling diethyl ether (2 × 50 mL). The ether
was evaporated to 10 mL, cooled to –6◦С, and the
precipitated solid was collected by filtration to give
off mixture of isomers (3.19 g, 70%). The isomers
were separated using silica gel chromatography.
1H (DMSO-d6, 300 MHz): δ 7.04 (t, 1H, J 8.1 Hz,
CHAr), 6.30 (dd, 2H, J1 2.4 Hz, J2 7.8 Hz, CHAr), 6.20
(m, 1H, CHAr), 2.89 (s, 12H, CH3), 2.78 (d, 24H, J
12 Hz, CH3).
13C (DMSO-d6, 125.8 MHz): δ 151.4 (d, J 148 Hz,
CN), 150.3 (d, J 20 Hz, C-1,3), 128.1 (C-2), 113.6
(C-6,4), 112.4 (C-5), 41.2 (d, J 1.25 Hz), 38.1. 31P
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of Bis- and Tris(3-H-1,3-azaphospholo)benzenes
7
TABLE 1 The Main Crystallographic Parameters of the
Compounds 18b and 12
6.4 (m, 1H, HAr), 2.71 (s, 6H, NCH3), 2.48 (d, 12H,
JPH 9Hz, NCH3), 2.4–2.5 (m, 52H, PNMe2, NMe2 +
SeP(NMe2)3); 13C NMR (125 MHz, C6D6) δ 176.46
(d, J = 23 Hz), 161.84 (d, J = 30 Hz), 160.31 (d, J =
9 Hz), 154.96 (d, J = 3.8 Hz), 128.70, 128.49, 127.88,
127.69, 127.50, 118.60 (d, J = 11.3 Hz), 114.19,
114.18, 114.14, 114.12, 111.84 (d, J = 2.5 Hz), 111.43,
41.47, 41.46, 41.34, 41.33, 41.25, 41.15, 39.24 (d, J =
9 Hz), 37.49 (d, (Me2N)3PSe J = 3.8 Hz).
Compound
18b
12
Cell parameters
˚
a [A]
10.9963(5)
12.5231(6)
21.6119(9)
90
90
90
2976.1(2)
23.8355(8)
8.0813(3)
10.9865(4)
90
˚
b [A]
˚
c [A]
α [◦]
β [◦]
γ [◦]
90
90
3
˚
V [A ]
2116.24(13)
N,N,Nꢁ,Nꢁ,Nꢁꢁ,Nꢁꢁ,Nꢁꢁꢁ,Nꢁꢁꢁ-Octamethyl-3,5-diselen-
oxo-3,5-dihydro-1,7-diaza-3λ5,5λ5-diphospha-s-inda-
cene-2,3,5,6-tetraamine 10 and N2,N2,N3,N3,N7,
N7,N8,N8 -Octamethyl-3,8-diselenoxo-3,8-dihydro-1,
6-diaza-3λ5,8λ5 -diphospha-as-indacene-2, 3, 7, 8-
tetraamine 11. Hexamethylphosphorus triamide
(990 mg, 6.1 mmol) was added to a solution of
compound 3 (1.28 g, 2.1 mmol) in benzene (5 mL).
The reaction mixture was kept for 20 h at room tem-
perature. The solvent was evaporated and then the
excess hexamethylphosphorus triamide was distilled
off in vacuo 0.05 Torr/100◦C. The residual oil (1.5 g)
exhibiting two main signals of P(III) compounds
8 and 9 in 31P NMR spectrum—57.52 and 56.14
as well as signal of tris(dimethylamino)phosphane
selenide 83.2 was dissolved in benzene (14 mL) and
finely ground selenium (500 mg, 6.3 mmol) was
added. The reaction mixture was stirred for 2 h at
60◦C. Excess selenium was filtered off; the solvent
was evaporated to give solid residue (1.11 g). The
solid was separated by silica gel chromatography
using ethylacetate as eluent.
Z
4
4
D [g·cm–3
]
1.347
1.345
Orthorhombic
Pna21
0.416
904
24 ≥ h ≥ −30
Crystal system
Orthorhombic
P212121
0.439
Space group
μ [сm−1
F(000)
Indices
]
1272
10≥ h ≥ −13
14 ≥ k ≥ −15 10 ≥ k ≥ −10
26 ≥ l ≥ −16
13 ≥ l ≥ −13
θmax [◦]
Number of reflections:
collected
independent
in refinement (I ≥ 3σ(I))
R(int)
Number of refined
parameters
26.59
26.68
15643
5917
4616
0.045
325
16689
4328
3252
0.061
235
Observed/Variable
Final R indices
R1 (F)
14.2
13.8
0.0532
0.0579
1.1139
1.33
0.0427
0.0416
1.1088
1.40
Rw (F)
GOF
Weighting coefficients
− 0.389
− 1.27
0.772
1.13
− 0.122
− 0.439
0.203
Compound 10 Rf 0.03–0.15; (0.72g, 66%), mp
258–260◦С. 31P (CDCl3): δ 53.02 (d, JPSe = 795 Hz),
52.85 (d, JPSe = 785 Hz). 1Н (CDCl3, 400 MHz): δ
7.28 (t, 1H, JHH 9.6 Hz, HAr), 6.76 (t, 1H, JHH 3.2 Hz,
HAr), 3.38 (s, 6H, NCH3), 3.24 (s, 6H, NCH3), 2.74 (d,
12H, JPH 12 Hz, NCH3).
Largest peak/hole
0.78/−0.64
0.37/−0.30
[e·cm−3
]
CCDC deposition number
933777
933776
(CDCl3): δ 67.5. MS (EI, 70eV): m/z (%) = 612.8
(98.95) [M]+.
13C NMR (125 MHz, CDCl3) δ 166.30 (d, J =
69 Hz), 161.42 (d, J = 2.5 Hz), 161.16 (d, J = 2.5 Hz),
127.68 (t, J = 16.3 Hz), 115.7 (d, J = 13.8 Hz), 114.76
(d, J = 13.8 Hz), 112.19 (t, J = 5.6 Hz), 39.03, 38.94,
38.93, 38.92, 36.76, 36.75, 36.73.
MS (EI, 70eV): m/z (%) = 523.0, 527.0, 528.9.
Anal. calcd for C16H26N6P2Se2 C 36.80, H 5.02, N
16.09, P 11.86. Found: C 36.32, H 4.61, N 16.41, P
12.05.
Nꢁ-[2,3-Bis(dimethylamino)-3H-1,3-benzazapho-
sphol-6-yl]-1,1-bis(dimethylamino)-N,N-dimethyl-
phosphinecarboximidamide 7 (The Mixture with Tris
(dimethylamino)-phosphane Selenide). Hexamethyl-
phosphorus triamide (990 mg, 6.1 mmol) was added
to a solution of compound 3 (1.28 g, 2.1 mmol)
in benzene (5 mL). The reaction mixture was kept
for 1 month at room temperature. The solvent was
evaporated under reduced pressure and then was
kept in vacuo 0.05 Torr maintaining temperature
below 20◦C. The residue was analyzed by NMR
spectroscopy.
Compound 11 Rf 0.3–0.4; (50 mg, 4%), mp 224–
226◦С. 31P (CDCl3): δ 54.33 (d, JPSe = 804 Hz), 54.30
(d, JPSe = 804 Hz), 51.62 (d, JPSe = 793 Hz), 51.59 (d,
1
JPSe = 793 Hz). Н (CDCl3, 400 MHz): δ 7.25 (dd,
31P (C6D6): δ 59, 95, 84. 1Н (C6D6, 500 MHz):
δ 7.40–7.36 (m, 1H, HAr), 7.16 (s, 1H, HAr), 6.6–
1H, JHH, 8 JPH 10 Hz, HAr), 6.68–6.58 (m, 1H, HAr),
3.42 (s, 3H, NCH3), 3.34 (s, 3H, NCH3), 3.21 (s, 6H,
Heteroatom Chemistry DOI 10.1002/hc

8
Marchenko et al.
NCH3), 2.73 (d, 6H, JPH 8 Hz, NCH3), 2.70 (d, 6H, JPH
8 Hz, NCH3). 13C NMR (125 MHz, CDCl3) δ 166.37
(d, J = 21.4 Hz), 165.78 (d, J = 30.2 Hz), 160.32 (d, J =
2.5 Hz), 160.10 (d, J = 2.5 Hz), 156.51 (d, J = 8.8 Hz),
156.25 (d, J = 8.8 Hz), 133.73 (d, J = 13.8 Hz), 115.48
(d, J = 7.5 Hz), 114.51 (d, J = 7.5 Hz), 114.37 (d,
J = 5 Hz), 114.28 (d, J = 3.8 Hz), 109.74 (d, J =
6.3 Hz), 108.88 (d, J = 7.5 Hz), 39.35, 38.97 (d, J =
2.5 Hz), 38.79, 38.75, 37.05 (d, J = 3.7 Hz), 36.62 (d,
J = 3.7 Hz), MS (EI, 70eV): m/z (%) = 522.0, 523.0,
529.0.
6.12, N 19.61, P 14.46. Found: C 44.45, H 6.29, N
19.38, P 14.12.
Nꢁ,Nꢁꢁꢁ,Nꢁꢁꢁꢁꢁ-Benzene-1,3,5-triyltris[N,N-dimethyl-
P-(trichloromethyl) (phosphonous diamide)] 14. A
solution of benzene-1,3,5-triamine 13 (670 mg,
5.4 mmol) and triethylamine (1.9 g, 18.8 mmol)
in pyridine (10 mL) was added to a solution of N,
N-dimethyl-P-(trichloromethyl) phosphonamidous
chloride (4.12 g, 17.9 mmol) in benzene (4mL).
The reaction mixture was stirred at 15◦С for 15 h.
The solvent was evaporated under reduced pressure
at 30◦С and to the residue, Et2O (70 mL) was
added. The insoluble residue was filtered off and
the mother liquor was evaporated under reduced
pressure. Then the product was extracted with
pentane (2 × 50 mL), the extract was evaporated
under reduced pressure to dryness and used in the
next step without further purification. Yield: 2.41g
(63.7%); mp: 35–40◦С. 31P NMR (Et2O), δ: 73.
Rf 0.5–0.7; (96 mg, 9%), mp 269–270◦С. 31P
(CDCl3): δ 54.20 (d, JPSe = 792 Hz), 54.17 (d, JPSe
792 Hz), 51.38 (d, JPSe = 782 Hz), 51.34 (d, JPSe
782 Hz).
=
=
1Н (CDCl3, 500 MHz): δ 7.28 (dd, 1H, JHH, 9
JPH 9 Hz, HAr), 6.74–6.64 (m, 1H, HAr), 3.45 (s, 3H,
NCH3), 3.37 (s, 3H, NCH3), 3.25 (s, 3H, NCH3), 3.24
(s, 3H, NCH3), 2.77 (d, 12H, JPH 13 Hz, NCH3). 13C
NMR (125 MHz, CDCl3) δ 166.72, 166.18, 165.55,
160.38 (d, J = 2.5 Hz), 160.15 (d, J = 2.5 Hz), 156.27
(d, J = 8.8 Hz), 156.01 (d, J = 10.1Hz), 133.70 (d,
J = 16.3 Hz), 115.38 (d, J = 7.5 Hz), 114.53 (d, J =
3.7 Hz), 114.45, 114.43, 114.41, 114.37 m, 110.37 (d,
J = 6.3 Hz), 109.53 (d, J = 6.3 Hz), 39.35 m, 38.99 (d,
J = 2.5 Hz), 38.73 (d, J = 3.8 Hz), 38.63 m, 37.03 (d, J
= 3.8 Hz), 36.90 (d, J = 5 Hz), MS (EI, 70eV): m/z (%)
= 522.9, 527.0, 528.9. Anal. calcd for C16H26N6P2Se2
C 36.80, H 5.02, N 16.09, P 11.86. Found: C 36.41, H
4.73, N 16.44, P 11.98.
Nꢁ,Nꢁꢁꢁ,Nꢁꢁꢁꢁꢁ-Benzene-1,3,5-triyltris[N,N-dimethyl-
P-(trichloromethyl)(phosphonosele-noic
diamide)]
15. To a stirred solution of 14 (2.4 g, 3.4 mmol) in
pyridine (10 mL), selenium (1.5 g, 10 mmol) was
added in one portion and the reaction mixture was
left at 15◦C for 72 h. The solvent was evaporated
under reduced pressure and the residue was washed
with H2O (20 mL) and MeOH (10mL), successively.
Then the isoluble residue was additionally washed
on filter with MeOH (5 × 10 mL) and dried to give 15
(1.97 g). The mother liquor was evaporated under
reduced pressure and the resulting residue was
triturated with H2O (10 mL) and MeOH (10 mL)
giving white solid 15 (0.25 g), combined yield 69%,
mp 140◦C (dec). 31P NMR (pyridine), δ: 71.5. 1Н
(CDCl3, 300 MHz), a mixture of three diastereomers
in a ratio of 1/0.9/2, δ: 7.02 (s, 1H, CHAr), 6.61 (s, 1H,
CHAr), 6.41 (s, 1H, CHAr), 5.166 (d, 3H, J 11.7 Hz,
3NH), 3.18 (d, 6H, J 10.8 Hz, NCH3), 3.16 (d, 6H, J
10.8 Hz, NCH3), 3.10 (d, 6H, J 10.8 Hz, NCH3). Anal.
calcd for C15H24Cl9N6P3Se3 N 8.97, P 9.91. Found:
N 9.32, P 10.21.
N, N, Nꢁ, Nꢁ, Nꢁꢁ, Nꢁꢁ,Nꢁꢁꢁ,Nꢁꢁꢁ-Octamethyl-3,5-dithi-
oxo-3,5-dihydro-1, 7-diaza-3λ5,5λ5-diphospha-s-inda-
cene-2,3,5,6-tetraamine 12. Hexamethylphospho-
rus triamide (410 mg, 2.5 mmol) was added to a
solution of compound 10 (522 mg, 1 mmol) in ben-
zene (10 mL). In 5 min, all volatiles were evaporated
in vacuo 0.05 Torr/150◦C. The residue was dissolved
in benzene (10 mL) and finely ground sulfur (65 mg,
2 mmol) was added. The reaction mixture was
heated at 40◦С with stirring till complete dissolution
of the sulfur. The solvent was evaporated under re-
duced pressure. The residue was recrystallized from
acetonitrile (1.5 mL) to give the target product 12
as yellow solid (120 mg, 28%), mp 310◦С (decomp.).
Nꢁ,Nꢁꢁ,Nꢁꢁꢁ-Benzene-1,3,5-triyltris[1,1-bis(dimethyl-
amino)-N, N-dimethylphosphinecar-boximidamide]
triselenide 16. A mixture of selenide 15 (1.9 g,
2 mmol) and condensed dimethylamine (9 mL) was
stirred for 20 h at 15◦С in a pressure tube. Then
the tube was opened allowing the dimethylamine
evaporating. The residue was washed with H2O
and dried under reduced pressure. The residue was
dissolved in benzene and treated with charcoal, fil-
tered, and evaporated under reduced pressure. The
residue was washed with hexane and recrystallized
1
31P (DMSO-d6): δ 61.6. Н (DMSO-d6, 300 MHz): δ
7.12–7.18 (m, 1H, HAr), 6.55 (t, 1H, J 3.6 Hz, HAr),
3.31 (s, 6H, P-NCH3), 3.16 (s, 6H, P-NCH3), 2.64 (d,
12H, J 12.3 Hz, NCH3). 13С (DMSO-d6): δ 166.8 (d,
J 78 Hz, C = N), 161.25 (d, J 4 Hz, 1,5-CAr), 161.0
(d, J 2.5 Hz, 1,5-CAr), 126.3–126.7 (m, 3-CAr), 114.3
(d, J 12.6 Hz, 2,4-CAr), 113.2 (d, J 13.8 Hz, 2,4-CAr),
110.7 (br s, 6-CAr), 38.2 (d, J 24 Hz, PNCH3), 35.11
(s, NCH3). MS (EI, 70eV): m/z (%) = 429.0 (92.5)
[M-H]+. Anal. calcd for C16H26N6P2S2 C 44.85, H
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of Bis- and Tris(3-H-1,3-azaphospholo)benzenes
9
from CH3CN (16 mL) to give 16 1.15g (65%). Mp
187–189◦С. 31P NMR (Et2O), δ: 65.1. 1Н (CDCl3,
500 MHz), δ: 5.71 (s, 3H, CHAr), 2.87 (s, 18H, NCH3),
2.30 (d, 36H, J 11.0 Hz, NCH3). 13C (CDCl3): δ 151.05
(d, J 147 Hz, CN), 150.2 (d, J 20 Hz, i-CAr), 105.7,
41.1 (d, J 2.5 Hz), 38.1 (d, J 1.3 Hz). Anal. calcd for
C27H57N12P3Se3 N 19.11, P 10.56. Found: N 19.45, P
10.73.
filtration. The mother liquor was evaporated under
reduced pressure and the residue was recrystallized
from CH3CN (25 mL) to give yellow solid (414 mg,
67%). Mp 330–332◦С. 31P (CDCl3): δ 59.7. 1Н (CDCl3,
300 MHz): δ 2.73 (dd, 18H, J1 9.0 Hz, J2 13.0 Hz,
NCH3), 3.23+3.24 (s, 9H, C-NCH3), 3.41+3.42 (s,
9H, C-NCH3).
Anal calcd. for C21H36N9P3S3 N 20.88, P 15.39.
Found: N 21.09, P 15.54.
N, N, Nꢁ, Nꢁ, Nꢁꢁ, Nꢁꢁ, Nꢁꢁꢁ, Nꢁꢁꢁꢁ, Nꢁꢁꢁꢁ, Nꢁꢁꢁꢁꢁ, Nꢁꢁꢁꢁꢁ, Nꢁꢁꢁꢁꢁ
Dodecamethyl-1,4,7-triaza-3,6,9-triphosphatrindene-
2,3,5,6,8hexaamine 17. To stirred solution
-
REFERENCES
a
of amidine 16 (2.93 g, 3.3 mmol) in benzene
(15 mL), hexamethylphosphorus triamide (1.96 g,
12 mmol) was added in one portion and the reaction
mixture was left at 15◦С for 5 min. Then, the
volatiles were removed under reduced pressure
and tris(dimethylamino)phosphane selenide was
distilled off in vacuo (bp 120–130◦С/ 0.05 mmHg).
The residue was placed in a pressure tube and
the product was extracted with pentane at 100◦С
(80 mL). The resulting solution was concentrated
to 50 mL and cooled to 17◦С to give an orange
precipitate. The precipitate was filtered and dried
under reduced pressure to give yellow solid 17
(1.0 g, 59%). 31P (C6D6, 202 MHz): δ 61.7, 61.4,
61.3. 1Н (C6D6, 300 MHz): δ 2.63, 2.67, 2.70 td,
2.61–2.72 m (18H, J 10.2 Hz, NCH3), 2.89 (9H, m,
NCH3), 2.99 (br s, 9H, NCH3).
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N, N, Nꢁ, Nꢁ, Nꢁꢁ, Nꢁꢁ, Nꢁꢁꢁ, Nꢁꢁꢁ, Nꢁꢁꢁꢁ, Nꢁꢁꢁꢁ, Nꢁꢁꢁꢁꢁ, Nꢁꢁꢁꢁꢁ
-
Dodecamethyl-3,6,9-trioxo-6,9-dihydro-3H-1,4,7-tri-
aza-3λ5,6λ5,9λ5-triphospha-trindene-2,3,5,6,8 hexaa-
mine 18a. To a stirred solution of 17 (100 mg,
0.2 mmol) in CH2Cl2 (2 mL), H2O2 (0.1 mL, 30%
aqueous) was added in one portion and the reaction
mixture was left at 17◦С for 10 min. The solvent was
evaporated under reduced pressure and the residue
was recrystallized from Et2O (5 mL) to give yellow
solid (21 mg, 20%). Mp 212–213◦С.
31P (CDCl3): δ 32.7 (88.5%); 18.8 (11.5%). 1Н
(CDCl3, 300 MHz): δ 2.62–2.72 (m, 18H, NCH3), 3.20
(m, 9H, C-NCH3), 3.34 (m, 9H, C-NCH3).
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Go¨ttingen, Germany, 1997.
N, N, Nꢁ, Nꢁ, Nꢁꢁ, Nꢁꢁ, Nꢁꢁꢁ, Nꢁꢁꢁ, Nꢁꢁꢁꢁ, Nꢁꢁꢁꢁ, Nꢁꢁꢁꢁꢁ, Nꢁꢁꢁꢁꢁ
-
Dodecamethyl-3,6,9-trithioxo-6,9-dihydro-3H-1,4,7-
triaza-3λ5,6λ5,9λ5-triphospha-trindene-2,3,5,6,8hexa
amine 18b. To a stirred solution of 17 (520 mg,
1.02 mmol) in benzene (6 mL), finely powdered
elemental sulfur (100 mg, 3.11 mmol) was added
in one portion and the reaction mixture was left at
70◦С for 1 h. After cooling to ambient temperature,
benzene (45 mL) was added to the reaction mix-
ture and insoluble components were separated by
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Heteroatom Chemistry DOI 10.1002/hc