SYNTHESIS OF AMINOMETHYLPHOSPHINES
901
nitrogen atoms, the reaction of compound IV with
methyl iodide gives a complex mixture of unidentified
products, probably formed by bond cleavage in the
triazaadamantyl fragments and in the diazaphosphori-
nane ring.
( P 26.74 ppm) in a 1:2 ratio. Crystallization of 1 g of
this mixture gave 0.37 g (13%) of pure compound I,
1
mp 213 214 C. IR spectrum, , cm : 3288 (N H),
1
1180 (P=O). H NMR spectrum, , ppm (J, Hz):
2
2.92 s (6H, C CH2 N), 3.16 d (2H, P CH2 N, JPH
2
9.3), 3.85 d (3H, N CHa N, JHH 12.0), 4.25 d (3H,
The main difference in the reactivity of 7-amino-
1,3,5-triazaadamantane and primary aromatic amines
toward bis(hydroxymethyl)phosphine is that in the
first case no 1,3,5,7-diazadiphosphacyclooctane is
formed even at a 1:1 reactant ratio, while with aro-
matic amines this type of derivatives is the most
stable [1, 8]. The 31P NMR spectra of the reaction
mixtures even after prolonged boiling in ethanol,
which generally favors conversion of aminomethyl
phosphine derivatives of diazadiphosphacyclooctanes
[8], contained no signals in the region of 50 ppm,
characteristic of the latter compounds. The only cyclic
aminomethylphosphine whose signal was observed in
the 31P NMR spectrum was diazaphosphorinane IV.
Besides, signals of various acyclic phosphines and
their oxidation products were present.
2
N CHb N, JHH 12.0), 7.03 7.95 m (10H, C6H5 P).
31P NMR spectrum (C6D6):
26.74 ppm. Found, %:
C 64.86, H 7.01, N 15.41,P P 8.08. C20H25N4OP.
Calculated, %: C 65.22, H 6.79, N 15.22, P 8.42.
Bis[(1,3,5-triazaadamantan-7-yl)aminomethyl]-
phenylphosphine (II). To a solution of 0.4 g of bis-
(hydroxymethyl)phenylphosphine in 15 ml of benzene,
0.72 g of 7-amino-1,3,5-triazaadamantane was added,
and the mixture was heated until the amine dissolved.
After cooling to room temperature, crystals of II
formed and were filtered off and washed with benzene
and acetone. An analytical sample was crystallized
from 1:1 benzene DMF. Yield 0.5 g (48%), mp
1
207 C. IR spectrum (Vaseline oil), , cm : 3280
(N H). 31P NMR spectrum (DMF):
26.61 ppm.
Found, %: C 60.08, H 8.21, N 25.08P, P 6.73. C22
H35N8P. Calculated, %: C 59.72, H 7.92, N 25.34,
P 7.01.
Inspite of these limitations, the reaction of 7-amino-
1,3,5-triazaadamantane with hydroxymethylphosphine
proved to be a more universal synthetic approach to
N-triazaadamantylaminomethylphosphines and their
derivatives, than the procedure based on N-triaza-
adamantylazomethines [7], and permitted to prepare
several new derivatives of four- and three-coordinate
phosphorus.
When crystallized in air, compound II oxidized to
give bis[(1,3,5-triazaadamantan-7-yl)aminome-
thyl]phenylphosphine oxide (III). mp 242 C.
31P NMR spectrum (DMF):
34.11 ppm. Found, %:
C 56.92, H 7.70, N 23.96, P P6.71. C22H35N8OP. Cal-
culated, %: C 57.64, H 7.64, N 24.45, P 6.77.
EXPERIMENTAL
1,3-Bis(1,3,5-triazaadamantan-7-yl)-5-phenyl-
1,3,5-diazaphosphorinane (IV). Paraform, 0.57 g,
was added to 0.7 g of phenylphosphine, and the mix-
ture was heated to on a water bath until homogeniza-
tion. The resulting bis(hydroxymethyl)phenylphos-
phine was mixed with 10 ml of benzene and 1.95 g
of 7-amino-1,3,5-triazaadamantane was added. The
reaction mixture was stirred for 15 min at room
temperature and then heated to the boil. A viscous
substance precipitated on walls of the flask. Its major
component was product IV. After cooling to room
temperature, the benzene solution was decanted and
evaporated to leave crystals of compound IV, which
The 31P NMR spectra were recorded on Bruker
WM-250 (101 MHz) and Bruker MSL-400 (161 MHz)
spectrometers. The H NMR spectra were obtained
on Bruker WM-250 (250 MHz) and Varian T-60 (60
MHz) spectrometers. The IR spectra of suspensions
in Vaseline oil were measured on Specord M-80 and
UR-20 spectrometers. All operations with phosphines
were carried out an inert atmosphere.
1
Dipheny[N-(1,3,5-triazaadamantan-7-yl)amino-
methyl]phosphine oxide (I). Diphenylphosphine,
1.4 g, was added to 0.23 g of formaldehyde, and the
reaction mixture was heated on an oil bath until homo- were filtered off and washed with benzene. The
genization (120 C). The resulting (hydroxymethyl)di-
phenylphosphine was dissolved in 10 ml of benzene,
1.16 g of 7-amino-1,3,5-triazaadamantane was added,
and the mixture was heated until the latter dissolved.
The crystals that formed on cooling (1.85 g) were
filtered off and washed with ether. By 31P NMR data,
they were a mixture of (hydroxymethyl)diphenylphos-
viscous substance remaining on walls of the flask was
crystallized from benzene to give pure IV. Both por-
tions of compound IV were combined. Yield 1.15 g
1
(40%), mp 198 C. H NMR spectrum (C6D6), , ppm
(J, Hz): 2.84 d.d (2H, P CHa N), 3.29 d.d (2H,
2
2
P CHe N, JHH 12.0, JPH 5.0), 3.34 s (12H, C CH2
N), 3.86 d (1H, N CH2 Nring, JHH 12.1), 4.08 d (7H,
2
2
phine (
17.7 ppm) and diphenyl[(1,3,5-triazaada-
N CHa Nad + N CHe Nring, JHH 12.0), 4.32 d (6H,
P
2
mantan-7-yl)aminomethyl]phosphine oxide (I)
N CHb Nad, JHH 12.0), 7.24 7.59 m (5H, C6H5 P).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 6 2001