Synthesis of new phosphines and P-heterocycles from phosphonates containing allyl group

Article abstract of DOI:10.1023/A:1023345313956

Addition of phenylphosphine to allylphosphonate followed by reduction of the resulting diphosphonate gives a new branched phosphine, bis(3-phosphinopropyl)phenylphosphine. Its reaction with paraform and p-toluidine yields oligomeric 3-[3-(propylenophenylphosphino)propyl]-1,5-di-p-tolyl-1,5,3, 7-diazadiphosphacyclooctane. Diethyl (5-allyl-2-ethoxybenzyl)phosphonate was obtained. Its reduction gives unsaturated (5-allyl-2-ethoxybenzyl)phosphine. This product adds two moles of formaldehyde to give bis-(hydroxymethyl)(5-allyl-2-ethoxybenzyl)phosphine. The reaction of this compound with p-toluidine yielded, depending on the conditions, the corresponding bis(aminomethyl)phosphine, 1,3,5-diazaphosphorinane, and 1,5,3,7-diazadiphosphacyclooctane, and also their derivatives containing allyl substituents.

Full text of DOI:10.1023/A:1023345313956

Russian Journal of General Chemistry, Vol. 72, No. 11, 2002, pp. 1754 1759. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 11, 2002,
pp. 1858 1863.
Original Russian Text Copyright
2002 by Baimukhametov, Zheltukhin, Nikonov, Balueva.
Synthesis of New Phosphines and P-Heterocycles
from Phosphonates Containing Allyl Group
F. Z. Baimukhametov, V. F. Zheltukhin, G. N. Nikonov, and A. S. Balueva
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received March 2, 2001
Abstract Addition of phenylphosphine to allylphosphonate followed by reduction of the resulting diphos-
phonate gives a new branched phosphine, bis(3-phosphinopropyl)phenylphosphine. Its reaction with paraform
and p-toluidine yields oligomeric 3-[3-(propylenophenylphosphino)propyl]-1,5-di-p-tolyl-1,5,3,7-diazadi-
phosphacyclooctane. Diethyl (5-allyl-2-ethoxybenzyl)phosphonate was obtained. Its reduction gives un-
saturated (5-allyl-2-ethoxybenzyl)phosphine. This product adds two moles of formaldehyde to give bis-
(hydroxymethyl)(5-allyl-2-ethoxybenzyl)phosphine. The reaction of this compound with p-toluidine yielded,
depending on the conditions, the corresponding bis(aminomethyl)phosphine, 1,3,5-diazaphosphorinane, and
1,5,3,7-diazadiphosphacyclooctane, and also their derivatives containing allyl substituents.
The interest in the preparation of new phosphonates
PhPH2 + 2(EtO)2P(O)Al
with unsaturated substituents is due to their con-
????, 80 C
siderable synthetic potential. In particular, these com-
PhP[(CH2)3P(O)(OEt)2]2
pounds can be readily converted into unsaturated
primary phosphines and then into functionalized
tertiary phosphines capable of copolymerization with
A
LiAlH4
PhP[(CH2)3PH2]2
I
organic oligomers, which is of interest for preparing
new polymeric materials. Also, starting from vinyl-
phosphonate, dendrimers containing up to 15 phos-
phine fragments were synthesized [1].
Trisphosphine I took up four molecules of form-
aldehyde on heating to 100 C to give bis[3-(dihy-
droxymethylphosphino)propyl]phenylphosphine B,
which further reacted with 2 mol of p-toluidine in
ethanol to give a mixture of oligomers of 3-[3 -(pro-
pylenophenylphosphino)propyl]-1,5-di-p-tolyl-1,5,3,7-
diazadiphosphacyclooctanes II. Similar oligo(diaza-
diphosphacyclooctanes) were recently prepared under
the similar conditions by the reactions of bis(dihy-
droxymethylphosphino)xylylene with primary aromatic
amines [2]. The IR spectrum of II contained the weak
bands of stretching vibrations of the terminal amino
and hydroxy groups, and the 31P NMR spectrum
In this connection, our goal was to prepare poly-
phosphines from phosphonates containing allyl groups.
As starting compounds we used diethyl allylphos-
phonate and previously unknown diethyl 5-allyl-2-
ethoxybenzylphosphonate.
Addition of phenylphosphine to two molecules of
diethyl allylphosphonate under homolytic conditions
[80 C, 2,2 -azobis(isobutyronitrile)] was virtually
quantitative. The reaction progress was monitored by
31P NMR spectroscopy. After 8 h, only the signals of
the bridging phosphorus atom at 26 ppm and
terminal phosphonate groups at 26 ppm in a 1:2 ratio
were observed. The resulting bis(3-diethoxyphos-
phorylpropyl)phenylphosphine A, without further
purification, was reduced with an excess of lithium
aluminum hydride to bis(3-phosphinopropyl)phenyl-
phosphine I, whose 31P NMR spectrum contained two
signals with the chemical shifts of 26 and 137 ppm
in a 1:2 ratio, belonging to the bridging tertiary and
terminal primary phosphorus atoms.
contained the signal at
26.88 ppm belonging to
the phosphino groups of tPhe bridging fragments and a
group of closely located signals at 48.3 ppm belong-
ing to the phosphorus atoms of diazadiphosphacyclo-
octane fragments. The characteristic phosphorus
chemical shifts in 1,5,3,7-diazadiphosphacyclooctanes
range from 48 to 52 ppm [2, 3].
To prepare diethyl (5-allyl-2-ethoxybenzyl)phos-
phonate III, we developed a multistage scheme includ-
ing the preparation of p-allylphenol and formation of
1070-3632/02/7211-1754$27.00 2002 MAIK Nauka/Interperiodica

SYNTHESIS OF NEW PHOSPHINES AND P-HETEROCYCLES
1755
2-diethylaminomethyl-4-allylphenol by the Mannich
reaction. The latter compound under relatively mild
conditions reacts with triethyl phosphite following the
Arbuzov reaction pattern to give compound III. The
by-product of this reaction is 5-allyl-2-ethoxy-2-oxo-
4CH2O
PhP[(CH2)3PH2]2
PhP[(CH2)3P(CH2OH)2]2
I
B
Tol-p
Ph
N
P
2p-TolNH2
5
P(CH2)3P(CH2)3
1,2 -oxaphosphindane IV. The amount of this com-
pound increases at overheating of the reaction mixture.
Products III and IV were separated by vacuum distilla-
tion.
N
Tol-p
n
II
H3PO4, CuCl2
HO
+ CH2=CH CH2Cl
All
HO
NaOH, NH3
(Et2N)2CH2
HNEt2
P(OEt)3
HNEt2
All
All
O
HO
(EtO)3P
Et2NCH2
All +
EtOP
All
O
HO
(EtO)2P(O)CH2
O
III
IV
However, an attempt to obtain the branched phos-
phine from more complex phosphonate III failed.
Though phenylphosphine readily added to this com-
pound in the presence of azobisisobutyronitrile (the
31P NMR spectra of the reaction mixture contained
only the signals of the bridging phosphino group at
26.59 ppm and terminal phosphonate groups at
25.45 ppm), after the reduction of adduct C the signal
of the bridging tertiary phosphino group disappeared.
Several signals in the range from 122 to 124 ppm
indicated cleavage of the bridging fragment. Probably,
the negative role was played by the tendency of aryl-
alkylphosphonates to the cleavage of the P C bond
under the conditions of reduction.
AIBN, 80 C
LiAlH4
(CH2)3
(CH2)3
PhPH2 + 2III
PhP
PhP
OEt
OEt
CH2P(O)(OEt)2
CH2PH2
2
2
C
At the same time, reduction of phosphonate III
gives 5-allyl-2-ethoxybenzylphosphine V in satisfac-
tory yield.
Phosphine V on careful heating to 100 110 C adds
two formaldehyde molecules to give the correspond-
ing bis(hydroxymethyl)(5-allyl-2-ethoxybenzyl)phos-
phine VI which, without further purification, was used
for preparing cyclic and acyclic aminomethylphos-
phines and their derivatives containing one or two
allyl groups capable of polymerization. For example,
the reaction of VI with two equivalents of p-toluidine
LiAlH4
III
EtO
All
H2PCH2
V
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

1756
BAIMUKHAMETOV et al.
in benzene yields bis(p-toluidinomethyl)(5-allyl-2-
ethoxybenzyl)phosphine D.
NMR spectrum of VII suggests the presence of two
p-tolyl and one 5-allyl-2-ethoxyphenyl fragments. The
signals of the methylene protons of ethoxy group and
P CH2 N and P CH2 Ar fragments overlap to give a
complex multiplet in the range 3.30 3.55 ppm. The
analytical data for VII are consistent with its
empirical formula.
In the 31P NMR spectrum of the reaction mixture,
the signal with the chemical shift
29.44 ppm,
belonging to compound D, was predoPminant, but we
failed to isolate this product pure. Therefore, we
converted crude phosphine D to the corresponding
phosphine sulfide VII by the reaction with elemental
sulfur. The IR spectrum of VII contains the charac-
teristic bands of stretching vibrations of the N H
Similarly to the case of bis(hydroxymethyl)aryl-
and bis(hydroxymethyl)benzylphosphines [2, 4], intro-
duction of an additional mole of formaldehyde into
this reaction leads to the closure of the six-membered
ring and formation of 1,3-di-p-tolyl-5-(5 -allyl-2 -
ethoxybenzyl)-1,3,5-diazaphosphorinane VIII, which
is stable to hydrolysis and oxidation with atmospheric
oxygen in the crystalline state and in solutions.
1
bonds at 3324 and 3408 cm , double bond of allyl
1
1
group at 1638 cm , and P=S bond at 700 cm . The
31P NMR spectrum contains one signal with the
chemical shift
49.55 ppm. The ratio of the integral
P
intensities of the corresponding signals in the 1H
OEt
2CH2O
V
CH2P(CH2OH)2
VI
All
H2NTol-p
2H2NTol-p
2H2NTol-p
CH2O
Tol-p
All
OEt
CH2P
Tol-p
Tol-p
OEt
CH2P
OEt
CH2P
VIII
N
N
NHTol-p
NHTol-p
PCH2
N
N
All
EtO
All
All
D
Tol-p
IX
H2O2
S
S
Tol-p
All
All
OEt
OEt
S
N
O
Tol-p
NHTol-p
NHTol-p
OEt
CH2P
All
CH2P
CH2P
PCH2
O
S
N
N
PCH2
EtO
All
All
VII
Tol-p
X
S
N
EtO
Tol-p
XI
The analytical data for VIII are consistent with its
empirical formula. No N H stretching bands are ob-
served in its IR spectrum, which confirms the cyclic
structure. In the 31P NMR spectrum, compound VIII
gives a signal at 39.94 ppm, which disagrees with
the values characteristic of the previously known 1,3-
diaryl-5-phenyl-1,3,5-diazaphosphorinanes (average
60 ppm [5]). The cause of the unusual chemical shift
of phosphorus is, most probably, the substitution of
the phenyl group by the functionalized benzyl group.
The H NMR spectrum confirms the suggested struc-
ture of VIII. For example, the ratio of the integral
intensities of the signals belonging to p-tolyl groups
(the singlet of methyl protons and AB system of
protons of phenylene fragments) and 5-allyl-2-ethoxy-
phenyl substituent (the triplet of methyl protons of
1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

SYNTHESIS OF NEW PHOSPHINES AND P-HETEROCYCLES
1757
ethoxy group, the doublet of methylene protons of
allyl group, the multiplet of the proton at the double
bond, and the doublet of the aromatic proton at C3)
X and XI in the 31P NMR spectra (39.73 and
45.71 ppm, respectively) are shifted downfield as
compared to the signals of 3,7-diphenyl-3,7-dioxo-
indicates the presence of two tolyl and one allylethoxy- (28 30
ppm)
and
3,7-diphenyl-3,7-dithioxo-
5
5
phenyl fragments in the molecule. Also, the doublet
of doublets of equatorial protons of the P CH2 N
1,5,3 ,7 -diazadiphosphacyclooctanes (36 38 ppm)
[7]. However, the IR and H NMR spectra of these
1
2
fragment at 3.39 ppm (2JHH 15.2 Hz, JPH 16.2 Hz)
compounds show that the heterocyclic structure is
preserved. In the IR spectra of the products X and XI,
the absorption bands of amino and hydroxy groups
and the doublet of doublets of the N CH2 N fragment
4
at 4.17 ppm (2JHH 13 Hz, JPH 2 Hz), characteristic of
1
phosphorinanes, are clearly identified in the spectrum.
The signals of axial protons of the P CH2 N and
N CH2 N fragments overlap with the signals of the
methylene protons of the ethoxy group and the ter-
minal protons of the double bond, respectively, and
form complex multiplets at 3.65 3.76 and 5.85
6.00 ppm. The nonequivalence of the methylene
protons of the heteroring shows that it has the chair
conformation. The signal of one of the P CH2 N
protons is obscured, which does not allow un-
ambiguous determination of the orientation of the
substituent at phosphorus. However, the coupling
are absent, and in the H NMR spectrum the ring
protons give a pattern typical of diazadiphosphacyclo-
octane derivatives: two doublets at 4.04 and 4.21 ppm
(2JHH 16.1 Hz) for disulfide XI and a doublet at
3.78 ppm (2JHH 15 Hz) and a doublet of doublets at
2
4.14 ppm (2JHH 15, JPH 5.2 Hz) for dioxide X. Small
2
values of JPH (0 5.2 Hz) are indicative of the equa-
torial orientation of the P=X bonds in both heterorings.
Thus, starting from diethyl allylphosphonate, we
prepared a new trisphosphine, bis(3-phosphinopropyl)-
phenylphosphine, and oligomers containing 1,5,3,7-
diazadiphosphacyclooctane fragments linked with
phosphine-containing bridges. Starting from diethyl
5-allyl-2-ethoxybenzylphosphonate, we prepared new
aminomethylphosphines and their derivatives con-
taining allyl groups. The presence of unsaturated
groups and the sufficient stability of these compounds
make them promising as comonomers in copoly-
merization with various organic monomers to give
new phosphorus-containing polymer materials.
2
constant JPH is close to that observed for 1,3-di-p-
e
tolyl-5-phenyl-1,3,5-diazaphosphorinane (2JPHe 16 Hz)
[6], for which the preferred equatorial orientation of
the substituent at phosphorus is known; this fact
suggests the similar conformation of diazaphosphori-
nane VIII also.
Reaction of compound VI with an equimolar
amount of p-toluidine in ethanol yielded the expected
1,5-di-p-tolyl-3,7-di(5-allyl-2-ethoxybenzyl)-1,5,3,7-
diazadiphosphacyclooctane IX. The absence of vibra-
tion bands of amino and hydroxy groups in the IR
spectrum of IX also counts in favor of its cyclic struc-
ture. Contrary to diazaphosphorinane VIII, compound
IX has the chemical shift of phosphorus characteristic
of 1,5,3,7-diazadiphosphacyclooctanes [2 4]
( 48.95 ppm). The 1H NMR spectrum of IX is typical
of diazadiphosphacyclooctanes. It shows that, in solu-
tions, this compound has the chair-chair conformation
with the equatorial orientation of substituents at phos-
phorus, characteristic of these heterorings. This
follows from the fact that the signal of axial protons
of the heteroring is a doublet of doublets at 3.76 ppm
EXPERIMENTAL
The IR spectra (mulls in mineral oil) were re-
corded on Specord M-80 and UR-20 spectrometers.
The 31P NMR spectra were taken on Bruker WM-250
(101 MHz) and Bruker MSL-400 (161 MHz) spec-
1
trometers. The H NMR spectra were measured on a
Bruker WM-250 spectrometer.
p-Allylphenol was prepared according to [8].
All manipulations with phosphines were carried out
in an inert atmosphere.
Bis(3-phosphinopropyl)phenylphosphine I.
A
2
with the coupling constant JHH 15.25 Hz and small
mixture of 2.78 g of phenylphosphine, 11.76 g of di-
ethyl allylphosphonate, and 0.15 g of azobis(isobu-
tyronitrile) was heated for 8 h at 80 C in a weak flow
of argon. A solution of the resulting bis[3-(diethoxy-
phosphoryl)propyl]phenylphosphine in 30 ml of abso-
lute diethyl ether was added dropwise to a suspension
of 1.58 g (10% excess) of LiAlH4 in 10 ml of ether
at a temperature not higher than 25 C. The tempera-
ture of the reaction mixture was gradually raised to
0 C, and the mixture was stirred for several hours.
Then the reaction mixture was treated with 3 ml of
2JPH (3.75 Hz), which corresponds to the dihedral
angle lone electron pair P C H close to 180 .
Phosphine IX is well soluble only in DMF and
DMSO, though its solubility is to some extent higher
than that of the previously known diazadiphospha-
cyclooctanes with phenyl groups at phosphorus.
Compound IX is stable against hydrolysis and oxida-
tion with atmospheric oxygen, but it is oxidized with
hydrogen peroxide and adds sulfur to form the cor-
responding dioxide X and disulfide XI. The signals of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

1758
BAIMUKHAMETOV et al.
degassed water at cooling with ice and then with 33
ml of 18% HCl. The organic layer was separated and
dried over MgSO4 for a day. The volatiles were
removed in a water-jet pump vacuum, and the residue
was fractionated in a vacuum. Yield of 0.56 g (7.81%),
bp 160 C (0.1 mm). 31P NMR spectrum, P, ppm:
26.5, 137 (1JPH 145 Hz).
the ether was fractionated in a vacuum. Yield of V
2.46 g (46%), bp 160 187 C (0.1 mm). 31P NMR
spectrum (C6H6), , ppm: 128.48 (1JPH 194 Hz).
Bis(p-tolylaminomethyl)(5-allyl-2-ethoxybenzyl)-
phosphine sulfide VII. Paraform, 0.334 g, was added
to 1.16 g of V, and the mixture was heated on a water
bath until it became homogeneous. A solution of
1.195 g of p-toluidine in 10 ml of benzene was added
to the resulting compound VI. The mixture was
stirred for a day at room temperature, the volatiles
were removed in a vacuum, and the residue was
treated with 0.18 g of sulfur in 10 ml of benzene. The
mixture was heated until sulfur dissolved. The next
day, the solvent was removed in a vacuum, and the
residue was crystallized from acetonitrile at 0 C. The
crystals were additionally recrystallized from aceto-
nitrile. Yield of VII 0.8 g (30%), mp 88 C. IR spec-
Oligo{3-[3 -(propyleno)phenylphosphino]propyl-
1,5-di-p-tolyl-1,5,3,7-diazadiphosphacyclooctane}
II. Paraform, 0.24 g, was added to 0.56 g of I, and
the mixture was heated until it became homogeneous.
The product was dissolved in 15 ml of absolute
ethanol, and 0.43 g of p-toluidine was added. The
reaction mixture was refluxed for several days until a
powder-like precipitate formed. It was filtered off and
dried for several hours in a vacuum (0.1 mm). Yield
of II 0.34 g (31%), mp 76 C. IR spectrum (mineral
1
1
oil), , cm : 796 (C Har), 984 (P Car), 1514 (C=Car),
trum (mull in mineral oil), , cm : 700 (P=S), 806
1620 (C=Car), 3025 (C Har). 31P NMR spectrum
(DMF), P, ppm: 26.88, 48.31. Found, %: C 70.34;
H 7.25; N 5.53; P 17.25. (C30H39N2P3)n. Calculated,
%: C 69.22; H 7.55; N 5.38; P 17.85.
(C Har), 1612 (C=Car), 1638 (C=C), 3324 (N H),
1
3408 (N H). H NMR spectrum (C6D6), ppm (J, Hz):
3
1.07 t (3H, OCH2CH3, JHH 6.7), 2.21 s (6H, CH3
3
C6H4), 3.25 d (2H, CH2CH=CH2, JHH 6.8), 3.30
3.55 m (8H, PCH2N, PCH2Ar, OCH2CH3), 4.39 br.s
(2H, NH), 5.04 5.12 m (2H, CH2CH=CH2), 5.89
Diethyl 5-allyl-2-ethoxybenzylphosphonate III.
p-Allylphenol, 53.78 g, was placed in a flask equipped
with a reflux condenser, 63.38 g of bis(diethyl-
amino)methane was added, and the mixture was left
for 3 days. The released diethylamine (22.1 g) was
removed in a water-jet pump vacuum at 60 C. The
residue was placed in a three-necked flask equipped
with an argon inlet tube, a thermometer, a descending
condenser, and a collector and filled with argon. Tri-
ethyl phosphite, 73 g (10% excess), was added. The
mixture was heated to 160 C (bath temperature
175 C), and 20 g of diethylamine was distilled off.
The residue was 2,2,2-triethoxy-5-allyl-1-oxa-2-phos-
3
6.06 m (1H, CH2CH=CH2), 6.47 d (4H, o-C6H4, JHH
3
9), 6.52 d (1H, C3Har, JHH 8.8), 6.96 d (4H, m-C6H4,
3
3JHH 8.8), 7.01 d (1H, C4Har, JHH 8.8). 31P NMR
spectrum, P, ppm: 49.54. Found, %: C 70.01; H 7.56;
N 5.65; P 6.09; S 6.91. C28H35N2OPS. Calculated, %:
C 70.30; H 7.32; N 5.86; P 6.49; S 6.69.
1,3-Di-p-tolyl-5-(5 -allyl-2 -ethoxybenzyl)-1,3,5-
diazaphosphorinane VIII. Paraform, 0.91 g, was
added to 2.11 g of V. The mixture was heated on a
water bath until it became homogeneous. The result-
ing solution of formaldehyde in VI was treated with a
solution of 2.17 g of p-toluidine in 15 ml of benzene.
The mixture was stirred for a day at room temperature,
the solvent was removed in a vacuum, and the residue
was crystallized from acetonitrile at 0 C. Yield of
VIII 1.9 g (40%), mp 106 C. IR spectrum (mull in
phaindane (
26 ppm). It was refluxed at 170 C for
P
12 h. The reaction progress was monitored by the 31P
5
NMR spectra. 5-Allyl-2-ethoxy-2-oxo-1,2 -oxaphos-
phindane IV ( 45 ppm) was formed along with III.
Compound III Pwas isolated by fractional distillation
in a vacuum; the fraction with bp 140 170 C
(0.2 mm) was collected. Yield 42.08 g (33%). 31P
NMR spectrum, P, ppm: 25.
1
mineral oil), , cm : 808 (C Har), 1424 (C N), 1512
1
(C=Car), 1619 (C=Car), 1638 (C=C). H NMR spec-
trum (C6D6), , ppm (J, Hz): 1.25 t (3H, OCH2CH3,
3JHH 6), 2.24 s (6H, CH3C6H4), 3.23 d (2H,
5-Allyl-2-ethoxybenzylphosphine V. A solution
of 8.01 g of I in 30 ml of absolute diethyl ether was
added dropwise to a suspension of 1.07 g (10%
excess) of lithium aluminum hydride in 40 ml of ether
at 30 C under dry argon. The mixture was stirred for
a day at room temperature, and then 2.03 ml of dis-
tilled degassed water and 23 ml of 18% HCl were
successively added dropwise with stirring and cooling
with ice. The organic layer was removed and dried
overnight over MgSO4. The residue after removing
3
CH2CH=CH2, JHH 6.5), 3.37 s (2H, P CH2Ar),
2
2
3.39 d.d (2H, PCHeN, JPH 16.2, JHH 15.2), 3.65
3.76 m (4H, PCHaN, OCH2CH3), 4.17 d.d (1H,
2
4
NCHeN, JHH 13, JPH 2), 4.95 5.11 m (3H, NCHaN,
CH2CH=CH2), 5.85 6.00 m (1H, CH2CH=CH2),
3
6.64 d (1H, C3Har, JHH 7.5), 6.90 7.30 m (C4Har,
C6Har), 6.99 d (o-C6H4, 3JHH 7), 7.07 d (m-C6H4, 3JHH
7) (total integral intensity 10H). 31P NMR spectrum, ,
ppm: 39.94. Found, %: C 75.71; H 8.36; N 6.45;
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

SYNTHESIS OF NEW PHOSPHINES AND P-HETEROCYCLES
1759
P 6.49. C29H38N2OP. Calculated, %: C 75.00; H 8.24;
N 6.00; P 6.72.
1,5-Di-p-tolyl-3,7-di(5 -allyl-2 -ethoxybenzyl)-3,7-
5
5
dithioxo-1,5,3 ,7 -diazadiphosphacyclooctane XI.
Sulfur, 0.039 g, and 5 ml of benzene were added to
0.41 g of IX. The mixture was heated until the re-
actants dissolved. The precipitate that formed after
cooling of the reaction mixture was filtered off,
washed with acetonitrile, and dried. Yield 0.2 g (44%),
1,5-Di-p-tolyl-3,7-di(5 -allyl-2 -ethoxybenzyl)-
1,5,3,7-diazadiphosphacyclooctane IX. Paraform,
1.23 g, was added to 4.27 g of V, and the mixture was
heated on a water bath until it became homogeneous.
The resulting compound VI was dissolved in 25 ml
of ethanol, and a solution of 2.23 g of p-toluidine in
20 ml of ethanol was added. The mixture was refluxed
on a water bath for 3 h. The white precipitate was
filtered off, washed with ethanol, and crystallized
from acetonitrile. Yield of IX 2.6 g (37%), mp 198
1
mp 115 C. IR spectrum (mull in mineral oil), , cm :
792 (C Har), 1616 (C=Car), 1640 (C=C), 3080
1
(C Har). H NMR spectrum (C6D6), , ppm (J, Hz):
3
0.99 t (6H, OCH2CH3, JHH 7), 2.11 s (6H, CH3
3
C6H4), 3.24 d (4H, CH2CH=CH2, JHH 6.5), 3.36 d
2
(4H, PCH2Ar, JPH 11.75), 3.54 q (4H, OCH2CH3,
1
200 C. IR spectrum (mull in mineral oil), , cm :
2
3JHH 7), 4.04 d (4H, PCHaN, JHH 16.1), 4.21 d (4H,
1
790 (C Har), 1614 (C=Car), 1638 (C=C). H NMR
2
PCHbN, JHH 16.1), 5.00 5.10 m (4H, CH2=CH),
spectrum (DMSO-d6), , ppm (J, Hz): 1.36 t (6H,
3
5.86 6.02 m (2H, CH2=CH), 6.50 d (2H, C3Har, JHH
3
OCH2CH3, JHH 6.9), 2.06 s (6H, CH3C6H4), 2.76 s
3
8), 6.90 7.05 m (C4Har), 6.94 d (o-C6H4, JHH 8.2),
3
3
(4H, PCH2Ar), 3.31 d (4H, CH2CH=CH2, JHH 6.3),
6.67 d (m-C6H4, JHH 8.2) (total integral intensity
2
2
10H), 7.40 s (2H, C6Har). 31P NMR spectrum (DMF),
P, ppm: 45.71. Found, %: C 70.41; H 7.56; N 3.63;
P 8.57; S 9.22. C42H52N2O4P2S. Calculated, %: C
70.99; H 7.32; N 3.94; P 8.73; S 9.01.
3.76 d.d (4H, PCHaN, JHH 15.25, JPH 3.75), 3.93
4.10 m (8H, OCH2CH3, PCHeN), 4.98 5.10 m (4H,
CH2=CH), 5.85 6.00 m (2H, CH2=CH), 6.04 d (4H,
3
3
o-C6H4, JHH 8.3), 6.67 d (4H, m-C6H4, JHH 8.3),
6.91 7.19 m (6H, C6H3). 31P NMR spectrum (DMF),
P, ppm: 48.97. Found, %: C 74.93; H 7.34; N 4.67;
P 8.75. C42H52N2O2P2. Calculated, %: C 74.34; H
7.67; N 4.12; P 9.14.
REFERENCES
1. Miedaner, A., Curtis, C.J., Barkley, R.M., and
Dubois, D.L., Inorg. Chem., 1994, vol. 33, no. 24,
p. 5482.
1,5-Di-p-tolyl-3,7-di(5 -allyl-2 -ethoxybenzyl)-3,7-
5
5
dioxo-1,5,3 ,7 -diazadiphosphacyclooctane X. To
a suspension of 0.2 g of IX in 3 ml of acetone, we
added a solution of 0.1 g of 33% H2O2 in 3 ml of
acetone. The mixture was stirred at room temperature
for 3 days. The precipitate was filtered off, washed
with acetone, and crystallized from DMF. Yield of X
1.99 g (95%), mp 245 250 C. IR spectrum (mull in
2. Musina, E.I., Kuznetsov, R.M., Nikonov, G.N., Balue-
va, A.S., and Gubanov, E.F., Zh. Obshch. Khim., 1999,
vol. 69, no. 6, p. 928.
3. Arbuzov, B.A., Erastov, O.A., Nikonov, G.N., Arshi-
nova, R.P., Romanova, I.P., and Kadyrov, R.A., Izv.
Akad. Nauk SSSR, Ser. Khim., 1983, no. 8, p. 1846.
1
4. Arbuzov, B.A. and Nikonov, G.N., Adv. Heterocyclic
Chem., 1994, vol. 61, no. 1, p. 59.
5. Arbuzov, B.A., Erastov, O.A., and Nikonov, G.N., Izv.
Akad. Nauk SSSR, Ser. Khim., 1979, no. 12, p. 2771.
mineral oil), , cm : 792 (C Har), 1184 (P=O), 1614
1
(C=Car), 1638 (C=C), 3072 (C Har). H NMR spec-
trum (DMSO-d6), , ppm (J, Hz): 1.30 t (6H, OCH2
3
CH3, JHH 7), 2.16 s (6H, CH3C6H4), 3.11 d (4H,
2
2
PCH2Ar, JPH 11.3), 3.78 d (4H, PCHaN, JHH 15),
3.99 q (4H, OCH2CH3, 3JHH 7), 4.14 d.d (4H, PCHeN,
6. Arbuzov, B.A., Erastov, O.A., Nikonov, G.N., Zyabli-
kova, T.A., Arshinova, R.P., and Kadyrov, R.A., Izv.
Akad. Nauk SSSR, Ser. Khim., 1986, no. 7, p. 1571.
2
2JHH 15, JPH 5.2), 4.98 5.11 m (4H, CH2=CH),
5.86 6.02 m (2H, CH2=CH), 6.76 7.12 m (14H,
7. Arbuzov, B.A., Erastov, O.A., Nikonov, G.N., Arshino-
va, R.P., and Kadyrov, R.A., Izv. Akad. Nauk SSSR,
Ser. Khim., 1980, no. 3, p. 721.
C6H4, C6H3). 31P NMR spectrum (in pyridine),
,
P
ppm: 39.73. Found, %: C 71.89; H 7.65; N 3.71; P
8.73. C42H52N2O4P2. Calculated, %: C 71.05; H 7.32;
N 3.94; P 8.72.
8. JPN Patent 56-6406, 1981, Ref. Zh. Khim., 1982,
5N105P.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002