Synthesis of new macrocyclic aminomethylphosphines based on 4,4'-diaminodiphenylmethane and its derivatives

Article abstract of DOI:10.1023/A:1015086419302

The reaction of bis(hydroxymethyl)phenylphosphine with 4,4'-diaminodiphenylmethane in DMF afforded 1,1',5,5'-bis[methylenedi(p-phenylene)]di(3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) (1) whose structure was established by X-ray diffraction analysis

Full text of DOI:10.1023/A:1015086419302

Russian Chemical Bulletin, International Edition, Vol. 51, No. 1, pp. 151—156, January, 2002
151
Synthesis of new macrocyclic aminomethylphosphines
based on 4,4´ꢀdiaminodiphenylmethane and its derivatives

R. M. Kuznetsov, A. S. Balueva, I. A. Litvinov, A. T. Gubaidullin, G. N. Nikonov, A. A. Karasik, and O. G. Sinyashin
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center of the Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843 2) 75 2253. Eꢀmail: anna@iopc.kcn.ru
The reaction of bis(hydroxymethyl)phenylphosphine with 4,4´ꢀdiaminodiphenylmethane
in DMF afforded 1,1´,5,5´ꢀbis[methylenedi(pꢀphenylene)]di(3,7ꢀdiphenylꢀ1,5ꢀdiazaꢀ3,7ꢀdiꢀ
phosphacyclooctane) (1) whose structure was established by Xꢀray diffraction analysis.
Sulfurization and oxidation of macrocyclic tetraphosphine 1 gave rise to products 2
and 3, respectively, compound 3 being obtained as a stable hexahydrate. The reaction of
bis(hydroxymethyl)phenylphosphine with bis(4ꢀNꢀmethylaminophenyl)methane in DMF folꢀ
lowed by sulfurization yielded monocyclic bis{methylenedi[pꢀphenylene(Nꢀmethyl)aminoꢀ
methyl]}di(Pꢀphenyl)phosphine sulfide (4).
Key words: macrocyclic aminomethylphosphines, Xꢀray diffraction analysis, 4,4´ꢀbis(hydrꢀ
oxymethyl)phenylphosphine, diaminodiphenylmethane.
Previously,1 it has been demonstrated that the reacꢀ
tions of primary aromatic diamines with bis(hydroxyꢀ
methyl)phosphines in EtOH afforded oligomers containꢀ
ing several diazadiphosphacyclooctane fragments. In the
preliminary communication,2 we have reported the synꢀ
thesis of the first representative of a new class of macrocyꢀ
clic aminomethylphosphines, viz., 1,1´,5,5´ꢀbis[meꢀ
thylenedi(pꢀphenylene)]di(3,7ꢀdiphenylꢀ1,5ꢀdiazaꢀ3,7ꢀ
diphosphacyclooctane) (1), based on the reaction of
bis(hydroxymethyl)phenylphosphine with 4,4´ꢀdiaminoꢀ
diphenylmethane in DMF. This result suggested that the
main type of the resulting oligomers depends primarily on
the structure of the diamine used as well as on the reacꢀ
tion conditions, in particular, on the nature of the solꢀ
vent. The presently known nitrogenꢀcontaining macrocyꢀ
clic phosphines3,4 are few in number and belong to monoꢀ
cyclic compounds. Macrocycle 1 is most structurally close
to 1,7,21,27ꢀtetraazaꢀ3,5,23,25ꢀtetraphosphaꢀ4,24ꢀdiꢀ
molybda[7.1.7.1]paracyclophane, which is also a macroꢀ
cyclic dimer containing the aminomethylphosphine and
diphenylmethane fragments.5 Macrocyclic tetraphosphine
1 is distinguished primarily by the cage structure. In this
connection, it was of interest to study its threeꢀdimenꢀ
sional structure in detail and to examine the possibility of
the formation of macrocyclic dimers in the reactions of
various hydroxymethylphosphines with diaminodiphenylꢀ
methane and its derivatives.
phosphine with 4,4´ꢀdiaminodiphenylmethane in a dilute
DMF solution at 80—100 °C. After cooling of the reacꢀ
tion mixture, compound 1 was isolated as a crystalline
precipitate (Scheme 1). As mentioned above, the reaction
performed in EtOH afforded a mixture of oligo(diꢀ
azaphosphacyclooctanes).1 Compound 1 was obtained as
white crystals with the distinct melting point. Dilution
of the reaction mixture and its additional stirring at
∼20 °C for 2 days allowed us to increase the yield of
macrocycle 1.
The IR spectrum of compound 1 has no absorption
bands of the terminal hydroxy and amino groups, which
are present in the starting compounds. The FAB mass
spectrum of compound 1 has a molecular ion peak at
m/z 932. The 31P NMR spectrum shows one signal at
δP –52.59. This chemical shift is close to those observed
for 1,5ꢀdiarylꢀ3,7ꢀdiphenylꢀ1,5ꢀdiazaꢀ3,7ꢀdiphosphaꢀ
cyclooctanes,6 which is evidence for the equivalence of
all the four phosphorus atoms and, consequently, for the
symmetrical structure of the macrocycle in solutions. This
is also confirmed by the 1H NMR spectroscopic data. The
methylene groups of both eightꢀmembered phosphorusꢀ
containing heterocycles are equivalent, and their signals
form an (AB)2X system typical of diazadiphosphacycloꢀ
octanes, viz., two doublet of doublets at δ 4.05 (2JHH
=
2
13.8 Hz, JPH = 13.8 Hz) and δ 4.49 (2JHH = 13.8 Hz,
2
2JPH = 3.5 Hz). The constants JPH are indicative of the
equatorial orientations of all substituents at the phosphoꢀ
rus atoms. The structure of macrocycle 1 was also estabꢀ
lished by Xꢀray diffraction analysis.
Results and Discussion
Macrocyclic tetraphosphine 1 was obtained as the maꢀ
jor product in the reaction of bis(hydroxymethyl)phenylꢀ
Molecule 1 is a centrosymmetrical "dimer" whose crysꢀ
tallographically independent portions each consist of one
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 142—147, January, 2002.
1066ꢀ5285/02/5101ꢀ151 $27.00 © 2002 Plenum Publishing Corporation

152
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 1, January, 2002
Kuznetsov et al.
Scheme 1
X = S, n = 0 (2); O, n = 6 (3)
eightꢀmembered diazadiphosphacyclooctane ring, two
benzene rings at the nitrogen atoms of the eightꢀmemꢀ
bered ring, and one bridging CH2 group (Fig. 1). The
eightꢀmembered heterocycles of molecule 1 adopt a
chair—chair (crown) conformation, the phenyl substituꢀ
ents at the phosphorus atoms are in the equatorial posiꢀ
tions, and the aromatic substituents at the nitrogen atoms
are in the axial positions. An analogous conformation of
the 1,5,3,7ꢀdiazadiphosphacyclooctane heterocycle was
also observed in the structure of 1,5,3,7ꢀtetraphenylꢀ1,5ꢀ
diazaꢀ3,7ꢀdiphosphacyclooctane.7 The principal geometꢀ
ric parameters of molecule 1 (the bond lengths and bond
angles; see Table 1) are identical (to within the experiꢀ
mental error) with those found in 1,5,3,7ꢀtetraphenylꢀ
1,5ꢀdiazaꢀ3,7ꢀdiphosphacyclooctane. The nitrogen atoms
in these compounds have a planarꢀtrigonal configuration
due to conjugation of the lone electron pairs with the
πꢀsystems of the benzene rings. This conjugation is reꢀ
sponsible for the fixation of the conformations of the
aromatic fragments at the nitrogen atoms and the rigid
conformation of the macrocycle as a whole. The bond
angle at the bridging C(17) atom (113.1(3)°) is somewhat
increased due, apparently, to the closure of the macroꢀ
cycle. The volume of the inner cavity of the macrocycle
accessible for solvate molecules is only 16 Å3, which is
insufficient even for a water molecule. The lone electron
pairs of the phosphorus atoms are located inside the
macrocycle, which is favorable for incorporation of small
metal ions (for example, alkali metal ions).
In the crystal of compound 1, there are four DMF
molecules of solvation per molecule 1. The methyl groups
of two DMF molecules reside in the macrocyclic cavity
on both sides (Fig. 2). Two other DMF molecules are
located outside the cavity and are involved in intermoꢀ
lecular C—H...O interactions with the protons of the
phenyl substituents (d(C(36)—O(81)) = 3.649(6) Å,
d(H(36)...O(81)) = 2.58(3) Å, ω(C(36)—H(36)...O(81)) =
171(2)°). In addition, the DMF molecules form intermoꢀ
lecular contacts with each other. It should be noted that
in the crystal packing of compound 1, the regions conꢀ
taining the solvate molecules are localized resulting in the
formation of alternating layers containing the macrocycles
and the DMF molecules, respectively (Fig. 3). The layers
are parallel to the crystallographic plane 0yz and the pheꢀ
nyl substituents of the macrocycles are located in the
Fig. 1. Crystal structure of macrocycle 1. The DMF molecules
of solvation are omitted.

New macrocyclic aminomethylphosphines
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 1, January, 2002
153
Table 1. Selected geometric parameters of the structure of 1
Bond
d/Å
Bond angle
ω/deg
Torsion angle
τ/deg
P(3)—C(2)
P(3)—C(4)
P(3)—C(31) 1.831(4)
P(7)—C(6)
P(7)—C(8)
P(7)—C(71) 1.811(4)
O(81)—C(81) 1.234(7)
O(91)—C(91) 1.21(1)
O(92)—C(92) 1.37(1)
N(1)—C(2)
N(1)—C(8)
N(1)—C(11) 1.389(5)
N(5)—C(4)
N(5)—C(6)
N(5)—C(51) 1.376(5)
N(80)—C(81) 1.298(7)
N(80)—C(82) 1.410(8)
N(80)—C(83) 1.421(8)
N(90)—C(91) 1.379(7)
N(90)—C(92) 1.397(9)
N(90)—C(93) 1.410(9)
1.872(4)
1.848(5)
C(2)—P(3)—C(4)
C(2)—P(3)—C(31)
C(4)—P(3)—C(31)
C(6)—P(7)—C(8)
C(6)—P(7)—C(71)
C(8)—P(7)—C(71)
C(2)—N(1)—C(8)
C(2)—N(1)—C(11)
C(8)—N(1)—C(11)
C(4)—N(5)—C(6)
C(4)—N(5)—C(51)
C(6)—N(5)—C(51)
P(3)—C(2)—N(1)
P(3)—C(4)—N(5)
P(7)—C(6)—N(5)
P(7)—C(8)—N(1)
C(81)—N(80)—C(82) 123.4(5)
C(81)—N(80)—C(83) 118.8(5)
C(82)—N(80)—C(83) 117.7(5)
C(91)—N(90)—C(92) 124.9(5)
C(91)—N(90)—C(93) 115.6(5)
C(92)—N(90)—C(93) 119.4(5)
C(14)—C(17)—C(54) 113.1(3)
100.0(2)
99.9(2)
98.3(2)
100.1(2)
100.5(2)
97.9(2)
118.6(3)
120.2(3)
121.2(3)
117.7(3)
123.2(3)
119.0(3)
113.1(3)
117.5(3)
113.5(3)
115.8(3)
C(4)—P(3)—C(2)—N(1)
C(31)—P(3)—C(2)—N(1)
C(2)—P(3)—C(4)—N(5)
C(31)—P(3)—C(4)—N(5) –177.3(3)
C(2)—P(3)—C(31)—C(32) –128.3(4)
C(2)—P(3)—C(31)—C(36)
C(4)—P(3)—C(31)—C(32) 130.0(3)
C(4)—P(3)—C(31)—C(36) –52.7(4)
C(8)—P(7)—C(6)—N(5)
C(71)—P(7)—C(6)—N(5)
C(6)—P(7)—C(8)—N(1)
C(71)—P(7)—C(8)—N(1) –177.5(3)
C(6)—P(7)—C(71)—C(72) 26.0(4)
C(6)—P(7)—C(71)—C(76) –153.0(4)
C(8)—P(7)—C(71)—C(72) –75.9(4)
C(8)—P(7)—C(71)—C(76) 105.1(4)
–80.3(3)
179.4(3)
81.1(3)
1.863(4)
1.854(4)
49.1(4)
–82.3(3)
177.6(3)
80.3(3)
1.459(5)
1.459(5)
1.432(5)
1.443(5)
C(8)—N(1)—C(2)—P(3)
C(11)—N(1)—C(2)—P(3) –74.8(4)
C(2)—N(1)—C(8)—P(7) –106.7(3)
107.5(3)
C(11)—N(1)—C(8)—P(7)
75.6(4)
C(2)—N(1)—C(11)—C(12) –179.6(4)
C(2)—N(1)—C(11)—C(16) –2.7(5)
C(8)—N(1)—C(11)—C(12) –1.9(5)
C(8)—N(1)—C(11)—C(16) 175.0(4)
C(6)—N(5)—C(4)—P(3) –107.0(3)
C(51)—N(5)—C(4)—P(3)
C(4)—N(5)—C(6)—P(7)
76.6(4)
107.7(3)
C(51)—N(5)—C(6)—P(7) –75.8(4)
C(4)—N(5)—C(51)—C(52) –5.2(6)
C(4)—N(5)—C(51)—C(56) 173.2(4)
C(6)—N(5)—C(51)—C(52) 178.4(4)
C(6)—N(5)—C(51)—C(56) –3.2(6)
layers formed by the solvate molecules. This mutual arꢀ
rangement of the molecules leads to the rather close crysꢀ
tal packing (the free volume of the unit cell is 65 Å3),
while the presence of a substantial amount of the solvent
in the crystal results in instability of molecules 1.
reaction performed in an ethanolic solution,1 its fraction
in a mixture of the reaction products (a mixture of oligoꢀ
mers) being variable.
Compound 1 exhibits the properties typical of usual
diazadiphosphacyclooctanes. Its treatment with elemenꢀ
tal sulfur in boiling DMF afforded the corresponding
tetraphosphine sulfide 2. The 31P NMR spectrum of comꢀ
pound 2 has one signal at δP 30.40, which is slightly shifted
upfield compared to the signals of monocyclic disulfides
of diazadiphosphacyclooctanes (cf. δP 36 10). In the
1H NMR spectrum of compound 2, the signals for the
protons of the methylene groups of the P—CH2—N fragꢀ
ments are observed as two doublets at δ 4.49 and 4.74
(2JHH = 15.5 Hz). In addition, the 1H NMR spectrum has
a singlet for the bridging methylene group at δ 3.56, two
doublets for the protons of the pꢀphenylene fragments at
δ 6.86 and 7.25 (3JHH = 8.5 Hz), and a multiplet for the
protons of the phenyl groups at δ 7.40—8.40. The integral
intensity ratio is 2 : 4 : 4 : 4 : 4 : 10. The small constants
2JPH (<2 Hz) observed for the protons of the heterocyclic
fragments are indicative of the equatorial orientation of
It can be assumed that the preferential formation of
the macrocycle of this type, which can be considered as a
"cyclic dimer", is associated with the spatial structure of
the starting diamine favorable for this process. A series of
macrocyclic diphosphonites8 and metallamacrocycles9
were prepared based on 4,4´ꢀdihydroxydiphenylmethanes
and their thio analogs. The synthesis of dimeric tetraꢀ
azatetraphosphadimolybdacyclophanes based on diaminoꢀ
diphenylmethane was also described.5 Apparently, the use
of DMF as the solvent prevents "premature" precipitation
of acyclic products and makes it possible to separate comꢀ
pound 1 from other reaction products. However, atꢀ
tempts to transform a mixture of oligo{5ꢀ[pꢀ(pꢀphenyleneꢀ
methyl)phenyl]ꢀ3,7ꢀdiphenylꢀ1,5ꢀdiazaꢀ3,7ꢀdiphosphaꢀ
cyclooctanꢀ1ꢀyls} into compound 1 by heating in DMF
failed. Probably, macrocycle 1 was also formed in the

154
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 1, January, 2002
a
Kuznetsov et al.
1186 cm–1, an intense broad stretching vibration band
of the hydroxy groups with the maximum (νmax) at
3400 cm–1, and a broad band with the maximum at
1660 cm–1 belonging, most likely, to bending vibrations
of the hydroxy groups of the water molecules. The
31P NMR spectrum of this compound has a signal at
δP 24.74 typical of diazadiphosphacyclooctane oxides,
which suggests that the skeleton of the molecule did not
undergo hydrolytic cleavage. The 1H NMR spectrum of a
solution of compound 1 in DMSOꢀd6 shows four groups
of signals, viz., a singlet of the bridging methylene group
at δ 3.71, a broad singlet of the methylene protons of the
diazadiphosphacyclooctane fragments at δ 4.42, an AB
system of the protons of the pꢀphenylene fragments at
δ 6.89 and 7.02 (3JHH = 8.15 Hz), and a multiplet of the
phenyl protons at δ 7.52—8.26; the intensity ratio is
2 : 8 : 4 : 4 : 10. Unfortunately, the signal for the methylꢀ
ene protons of the heterocyclic fragments is generated,
which does not allow us to judge the predominant conforꢀ
mation of the molecule in solution. Taking into account
also the data from elemental analysis, the structure of
1,1´,5,5´ꢀbis[methylenedi(pꢀphenylene)]di(3,7ꢀdioxoꢀ
3,7ꢀdiphenylꢀ1,5ꢀdiazaꢀ3,7ꢀdiphosphacyclooctane) hexaꢀ
hydrate (3) was assigned to the product of oxidation of
compound 1. Hexahydrate 3 is a very stable compound.
Water is retained in the compound both upon recrystalliꢀ
zation from DMSO and upon prolonged drying in vacuo.
In spite of the presence of the hydrophilic fragments,
compound 3 is insoluble in water and its mixtures with
organic solvents.
b
Fig. 2. Mutual arrangement of the molecules of DMF and 1 in
the crystal structure: a, a view along the direction close to the
crystallographic axis 0х; b, a view along the crystallographic
axis 0y. The hydrogen bond is indicated by a dashed line.
Attempts to prepare analogous macrocyclic tetraꢀ
phosphines based on 4,4´ꢀdiaminodiphenylmethane and
other bis(hydroxymethyl)phosphines, viz., bis(hydroxyꢀ
methyl)mesitylphosphine and bis(hydroxymethyl)(5ꢀallylꢀ
2ꢀethoxybenzyl)phosphine, failed. In both cases, the reꢀ
actions afforded mixtures of cyclic and linear oligomers
and neither fractional crystallization nor reprecipitation
allowed us to isolate the target macrocyclic phosphines.
The compounds cannot also be separated by chromatoꢀ
graphic methods due to their low solubility. Hence, the
difference in the solubility of macrocyclic aminomethylꢀ
phosphines and acyclic oligomeric compounds formed as
byꢀproducts is of great (probably, decisive) importance in
obtaining the desired compounds in the pure form.
the P=S bonds. Apparently, the eightꢀmembered ring in
compound 2, like that in 1,5ꢀdiꢀpꢀtolylꢀ3,7ꢀdiphenylꢀ3,7ꢀ
dithioꢀ1,5ꢀdiazaꢀ3,7ꢀdiphosphacyclooctane,10 adopts a
distorted boat—boat conformation. Oxidation of macroꢀ
cyclic phosphine 1 with aqueous H2O2 in acetone gave
rise to a white crystalline compound whose IR spectrum
has a stretching vibration band of the phosphoryl group at
c
0
b
The importance of this factor was confirmed by the
results of the synthesis of a monocyclic macrocycle
based on the diaminodiphenylmethane derivative, viz.,
bis[4ꢀ(Nꢀmethylamino)phenyl]methane. Refluxing of
bis(hydroxymethyl)phenylphosphine in MeCN afforded
a complex mixture of lowꢀmolecularꢀweight oligomeric
aminomethylphosphines. To increase the yield of the macꢀ
rocyclic compounds, we carried out the reaction in DMF,
which was ∼2.5 times more dilute than that used in the
synthesis of compound 1. It should be noted that even
this rather small decrease in the concentration of the reꢀ
a
Fig. 3. Layered structure in the crystal of compound 1. Only
solvate DMF molecules are shown.

New macrocyclic aminomethylphosphines
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 1, January, 2002
155
agents led to substantial deceleration of the process and
the reaction was completed only upon prolonged heating
of the mixture at 100 °C (25 h instead of 3ꢀ4 h in the
synthesis of macrocycle 1). In the 31P NMR spectrum of
the reaction mixture, the predominant signal is observed
at δP –39.15 and corresponds, apparently, to a macrocyꢀ
clic product. We succeeded in separating the latter from
impurities of other oligomers only by converting it into
the corresponding diphosphine disulfide. After the reꢀ
moval of the solvent, extraction of the residue folꢀ
lowed by fractional crystallization afforded bis{methyleneꢀ
di[pꢀphenylene(Nꢀmethyl)aminomethyl]}di[(Pꢀpheꢀ
nyl)phosphine sulfide] (4) in very low yield (3.4%). This
low yield is, evidently, explained by large losses in the
course of purification due to the insignificant difference
in solubility of macrocycle 4 and other oligomers. Chroꢀ
matographic separation did not meet with success as well.
To summarize, the reactions of bis(hydroxymeꢀ
thyl)phenylphosphine with 4,4´ꢀdiaminodiphenylmethane
and its N,N´ꢀdimethyl derivative afforded previously unꢀ
known macrocyclic compounds with the structures of cyꢀ
clic "dimers" as the major products.
Experimental
The 31P NMR spectra were recorded on a Bruker MSLꢀ400
spectrometer (161 MHz, 85% H3PO4 as the external standard).
The 1H NMR spectra were measured on a Bruker WMꢀ250
spectrometer (250 MHz). The IR spectra were recorded on a
Specord Mꢀ80 spectrometer (Nujol mulls). All operations with
phosphines were carried out under an inert atmosphere. The
FAB mass spectra were obtained on a Finnigan MAT TSQꢀ700
mass spectrometer.
Xꢀray diffraction study of compound 1. Crystals of a solvate of
1 with four DMF molecules, 1•4C3H7NO, M = 1225.38,
are orthorhombic. At 20 °C, а = 21.526(2), b = 14.658(4),
c = 21.793(3) Å, V = 6876.4 Å3, dcalc = 1.18 g cm–3, Z = 4, space
group Pbca (molecule 1 occupies a special position, viz., a cenꢀ
ter of symmetry). The unit cell parameters and the intensities of
8271 reflections (of which 3719 reflections were with I = 3σ)
were measured on an automated fourꢀcircle EnrafꢀNonius
CADꢀ4 diffractometer (λMoꢀKα, graphite monochromator,
ω/2θ scanning technique, θ ≤ 26.3°). The linear correction was
applied to the intensities of the measured reflections based on
the decrease in the intensities of three check reflections (34%
decrease in the course of Xꢀray data collection). Absorption was
Scheme 2
ignored (µ = 1.56 cm–1). The structure was solved by direct
Mo
methods using the SIR program11 and refined first isotropically
and then anisotropically. The oxygen atom of one of the solvate
dimethylformamide molecules is disordered over two positions
with equal occupancies (0.5). At the final stage, the positions of
the hydrogen atoms were revealed from difference electron denꢀ
sity syntheses (except for the H atoms of the disordered fragꢀ
ments) and refined isotropically. The final reliability factors
were as follows: R = 0.048, Rw = 0.055 using 3363 independent
reflections with F 2 ≥ 3σ. All calculations were carried out on a
DEC Alpha Station 200 using the MolEN program package.12
The atomic coordinates, bond lengths, bond angles, and therꢀ
mal parameters were deposited with the Cambridge Strucꢀ
tural Database (Cambridge Crystallographic Data Centre,
CCDC 1135/63).
1,1´,5,5´ꢀBis[methylenedi(pꢀphenylene)]di(3,7ꢀdiphenylꢀ
1,5ꢀdiazaꢀ3,7ꢀdiphosphacyclooctane) (1). Solid paraformaldeꢀ
13
Like analogous sulfide 2, macrocycle 4 is a poorly
soluble highꢀmelting crystalline compound. Its IR specꢀ
trum has no vibration bands of the terminal hydroxy and
amino groups, and its 31P NMR spectrum shows one
signal at δP 40.03. The 1H NMR spectrum of compound 4
provides indirect evidence for its cyclic structure because
the protons of the methylene groups of the P—CH2—N
fragments are nonequivalent and give an AB system, viz.,
hyde (0.38 g, 12.66 mmol) was added to PhPH2
(0.69 g,
6.27 mmol) and the reaction mixture was heated on a water
bath until the mixture became homogeneous. Bis(hydroxyꢀ
methyl)phenylphosphine that formed was dissolved in degassed
DMF (15 mL), which was preliminarily dried and distilled over
fused K2CO3, and then a solution of 4,4´ꢀdiaminodiphenylꢀ
methane (0.62 g, 3.13 mmol) in DMF (15 mL) was added. The
reaction mixture was stirred at 100 °C for 3.5 h and then at
∼20 °C for 2 days. The precipitate that formed was filtered off,
washed successively with DMF and MeCN, and dried at 0.1 Torr
for 2 h. Compound 1 was obtained in a yield of 0.75 g (51%),
m.p. 210 °C. Found (%): C, 74.05; H, 5.99; N, 6.22; P, 12.87.
2
two doublets at δ 4.20 and 4.32 with JHH = 15.75 Hz;
2JPH ≈ 0. The cyclic structure of dimer 4 was confirmed by
its FAB mass spectrum containing the corresponding moꢀ
lecular ion peak at m/z 784 (100%).
C
58H56N4P4. Calculated (%): C, 74.68; H, 6.01; N, 6.01;

156
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 1, January, 2002
Kuznetsov et al.
P, 13.30. 1H NMR (DMSOꢀd6), δ: 3.48 (s, 4 H, CH2); 4.05 (dd,
pound 4 was obtained in a yield of 0.042 g (3.4%), m.p.
242—246 °C. Found (%): C, 69.82; H, 6.18; N, 6.97; P, 7.93;
S, 8.34. C46H50N4P2S2. Calculated (%): C, 70.41; H, 6.37;
N, 7.14; P, 7.90; S, 8.16. 1H NMR (DMSOꢀd6), δ: 2.75 (s,
2
2
8 H, P—CHe—N, JHH = 13.8 Hz, JPH = 13.8 Hz); 4.49 (dd,
2
2
8 H, P—CHa—N, JHH = 13.8 Hz, JPH = 3.5 Hz); 6.50 (d,
3
8 H, orthoꢀC6H4, JHH = 8.6 Hz); 7.07 (d, 8 H, metaꢀC6H4,
3JHH = 8.6 Hz); 7.40—7.70 (m, 20 H, C6H5). 31P NMR (DMF),
δ: –52.59. MS (FAB+, Xe, 7 kV), m/z (Irel (%)): 932 [M+]+ (100).
1,1´,5,5´ꢀBis[methylenedi(pꢀphenylene)]di(3,7ꢀbis(thioxo)ꢀ
3,7ꢀdiphenylꢀ1,5ꢀdiazaꢀ3,7ꢀdiphosphacyclooctane) (2). A mixture
of compound 1 (0.25 g, 0.27 mmol), S8 (0.034 g, 1.06 mmol),
and DMF (10 mL) was heated until the solid compounds were
dissolved. After 16 h, the precipitate was filtered off, washed
with MeCN, and dried at 0.1 Torr for 2 h. Compound 2 was
obtained in a yield of 0.2 g (70%), m.p. 218—220 °C. Found (%):
C, 65.31; H, 5.37; N, 5.52; P, 12.01; S, 12.41. C58H56N4P4S4.
Calculated (%): C, 65.66; H, 5.28; N, 5.28; P, 11.70; S, 12.08.
1H NMR (DMSOꢀd6), δ: 3.56 (s, 4 H, CH2); 4.49 (d, 8 H,
12 H, NMe); 3.64 (s, 4 H, CH2); 4.20 (d, 4 H, P—CHA—N,
2
2JHH = 15.8 Hz); 4.32 (d, 4 H, P—CHB—N, JHH
=
3
15.8 Hz); 6.64 (d, 8 H, orthoꢀC6H4, JHH = 8.9 Hz); 6.89 (d,
3
8 H, metaꢀC6H4, JHH = 8.9 Hz); 7.37—8.10 (m, 10 H,
C6H5). 31P NMR (DMSO), δ: 40.03. MS (FAB+, Xe, 7 kV),
m/z (Irel (%)): 784 [M+]+ (100).
References
1. E. I. Musina, R. M. Kuznetsov, E. F. Gubanov, A. S.
Balueva, and G. N. Nikonov, Zh. Obshch. Khim., 1999, 69,
928 [Russ. J. Gen. Chem., 1999, 69 (Engl. Transl.)].
2. A. S. Balueva, R. M. Kuznetsov, I. A. Litvinov, A. T.
Gubaidullin, and G. N. Nikonov, Mendeleev Commun.,
2000, 120.
3. L. Wey, A. Bell, I. D. Williams, and S. J. Lippard, J. Am.
Chem. Soc., 1986, 108, 8302.
4. C. W. G. Ansell, M. K. Cooper, K. P. Dancey, P. A.
Duckworth, K. Henrik, M. McPartlin, and P. F. Tasker,
J. Chem. Soc., Chem. Commun., 1985, 439.
5. E. Lindner, M. Mohr, C. Nachtigal, R. Fawzi, and
G. Henkel, J. Organomet. Chem., 2000, 595, 166.
6. B. A. Arbuzov, O. A. Erastov, G. N. Nikonov, I. P.
Romanova, and R. A. Kadyrov, Izv. Akad. Nauk SSSR, Ser.
Khim., 983, 32, 1846 [Bull. Acad. Sci. USSR, Div. Chem. Sci.,
1983, 32, 1672 (Engl. Transl.)].
7. B. A. Arbuzov, O. A. Erastov, G. N. Nikonov, I. A. Litvinov,
D. S. Yufit, and Yu. T. Struchkov, Dokl. Akad. Nauk SSSR,
1981, 257, 127 [Dokl. Chem., 1981 (Engl. Transl.)].
8. Yu. I. Blokhin, D. Gusev, V. K. Belski, A. I. Stash, and E. E.
Nifantiev, Phosphorus, Sulfur, Silicon, Relat. Elem., 1995,
102, 143.
2
P—CHA—N, JHH = 15.5 Hz); 4.74 (d, 8 H, P—CHB—N,
2JHH = 15.5 Hz); 6.86 (d, 8 H, orthoꢀC6H4, 3JHH = 8.5 Hz); 7.25
3
(d, 8 H, metaꢀC6H4, JHH = 8.5 Hz); 7.40—8.40 (m, 20 H,
C6H5). 31P NMR (DMSO), δ: 30.40.
1,1´,5,5´ꢀBis[methylenedi(pꢀphenylene)]di(3,7ꢀdioxoꢀ3,7ꢀ
diphenylꢀ1,5ꢀdiazaꢀ3,7ꢀdiphosphacyclooctane) (3). A 30% H2O2
aqueous solution (0.07 mL, 0.62 mmol) was added to a suspenꢀ
sion of compound 1 (0.12 g, 0.13 mmol) in acetone (5 mL) and
the reaction mixture was stirred at ∼20 °C for 16 h. Then the
precipitate that formed was filtered off, washed with Et2O, and
dried at 0.1 Torr for 2 h. Compound 3 was obtained in a yield of
0.14 g (98%), m.p. 250—253 °C. Found (%): C, 63.10; H, 5.81;
N, 5.29; P, 10.96. C58H56N4P4O4•6H2O. Calculated (%):
C, 63.04; H, 6.16; N, 5.07; P, 11.23. IR, ν/cm–1: 3410 (OH);
1650 (H2O); 1186 (P=O). 1H NMR (DMSOꢀd6), δ: 3.71 (s, 4 H,
CH2); 4.42 (br.s, 16 H, P—CH2—N); 6.89 (d, 8 H, orthoꢀC6H4,
3
3JHH = 8.2 Hz); 7.02 (d, 8 H, metaꢀC6H4, JHH = 8.2 Hz);
7.52—8.26 (m, 20 H, C6H5). 31P NMR (DMSO), δ: 24.74.
Bis{methylenedi[pꢀphenylene(Nꢀmethyl)aminomeꢀ
thyl]}di[Pꢀ(phenyl)phosphine sulfide] (4).
A solution of
bis[4ꢀ(Nꢀmethylamino)phenyl]methane (0.72 g, 3.18 mmol) in
DMF (15 mL) was added to a solution of PhP(CH2OH)2 (0.54 g,
3.18 mmol) (see the synthesis of 1) in dry degassed DMF
(15 mL). The reaction mixture was stirred at 100 °C for 25 h and
cooled to ∼20 °C. Then sulfur (0.11 g, 3.43 mmol) was added
and the reaction mixture was heated until the sulfur was disꢀ
solved. After 16 h, the solvent was removed in vacuo, the residue
was extracted with a 1 : 2 mixture (15 mL) of MeCN and acꢀ
etone on refluxing for 0.5 h. The adhesive precipitate, which was
obtained after cooling of the extract, was recrystallized from
DMF. The initially formed fine precipitate, which consisted of
compound 4 and impurities of acyclic oligomers, was separated
after which paleꢀyellow crystals of compound 4 precipitated
from the mother liquor upon storage. The crystals were filtered
off, washed with MeCN, and dried at 0.1 Torr for 3 h. Comꢀ
9. C. G. Arena, D. Drommi, F. Faraone, C. Graiff, and
A. Tiripicchio, Eur. J. Inorg. Chem., 2001, 247.
10. B. A. Arbuzov, O. A. Erastov, G. N. Nikonov, D. S. Yufit,
and Yu. T. Struchkov, Dokl. Akad. Nauk SSSR, 1982, 267,
650 [Dokl. Chem., 1982 (Engl. Transl.)].
11. A. Altomare, G. Cascarano, C. Giocovazzo, and D. Viterbo,
Acta Crystallogr., Sect. A, 1991, 47, 744.
12. L. H. Straver and A. J. Schierbeek, MolEN. Structure Deterꢀ
mination System. Nonius B., 1994, 1, 2.
13. V. V. Kormachev and M. S. Fedoseev, Preparativnaya
khimiya fosfora [Preparative Chemistry of Phosphorus], Izdꢀvo
UrO RAN, Perm, 1992, 22 (in Russian).
Received April 10, 2001;
in revised form July 19, 2001