880
ZAKHAROV et al.
ninhydrin) or as orange or pink spots on a white
background (with Dragendorf reagent).
iodine vapor followed by treatment with water. With
sufficiently strong bases, such as diethylamine and
piperidine (pKa 10 11), the reaction was complete
within this time. With weaker bases, such as morpho-
line, oligooxyethylene- , -diamines, ethanolamine
derivatives, etc. (pKa 6 8), removal of the solvent
from the reaction mixture and additional heating of
the residue at 130 135 C for 3 4 h was needed with
subsequent dilution of the brown residue with benzene.
Sodium bicarbonate, 500 mg, was added to the result-
ing brown solution, and it was refluxed with stirring
for 10 15 min to remove the catalyst. After cooling,
the precipitate of sodium salts was filtered off through
a folded filter and washed with benzene (3 7 ml).
The combined filtrates were evaporated on a rotary
evaporator to remove the solvent, and the residue was
fractionated in a vacuum (0.15 0.20 mm Hg). The
yield of the target -aminothiophosphonates by this
procedure was 50 60%.
N,N -Bis(diamylphosphinoyl)-N,N -dibutyl-2,11-
diaza-5,8-dioxadodecane (XLVIII). To a mixture of
3.8 g of freshly distilled diamyl(N-butylaminomethyl)-
phosphine oxide, 20 ml of dimethylamine-free DMF,
and 0.91 g of anhydrous finely ground potassium
carbonate, a solution of 1.83 g of freshly distilled
1,8-dibromo-3,6-dioxaoctane in 5 ml DMF was added
dropwise with stirring at 50 55 C over the course of
0.5 h. The resulting mixture was stirred for 2.5 h.
Over this period, it was gradually heated to 70 C and
then stirred on a boiling water bath for 2 h, cooled,
and poured in 100 ml of water, and extracted with
methylene chloride (6 10 ml). The combined organic
extracts were washed with 15 ml of water and dried
over anhydrous sodium sulfate. The solvent was re-
moved in a vacuum to give 4.13 g (90%) of a crude
product as a yellow oil. This oil crystallized on
handling to form a yellowish crystalline material, mp
O,O-Dibutyl-(N-piperidinomethyl)thiophos-
phonate. 1H NMR spectrum, , ppm: 0.8 1.05 m (6H,
butyl CH3), 1.3 1.8 m [14H, butyl (CH2)2 and pipe-
ridyl C3H2, C4H2, and C5H2], 3.90 4.18 m (4H, butyl
35 37 C,
43 ppm. According to TLC data, this
P
material was practically free of admixtures of the
starting reagents, but, if necessary, it can be purified
by column chromatography, eluent chloroform
acetone (4:1).
2
CH2O), 3.06 d (2H, P CH2 N, JHP 10.1 Hz), 2.35
2.65 m (4H, piperidyl CH2N).
1-(Dioctylphosphinoyl)-1-(N-piperidino)cyclo-
hexane (LIII) was prepared by mixing of equimolar
reagent amounts with a catalytic amount of p-toluene-
sulfonic acid without solvent. The reaction mixture
was heated at 140 C in an inert atmosphere and then
diluted with toluene, and washed with a dilute sodium
bicarbonate solution and water. The organic phase was
dried over magnesium sulfate. The solvent was
removed in a vacuum, the residue was dissolved in a
minimum of boiling hexane, and the hot solution was
filtered and left for 3 days in a freezer. The crystals
that formed were filtered off, washed with dry hexane,
and dried in air. The -aminophosphoryl compound
was obtained as a slightly yellowish crystalline
ACKNOWLEDGMENTS
The work was financially supported by the Univer-
sities of Russia Basic Research Scientific and
Engineering Program and the Materials and Techno-
logies of XXI Century Scientific and Educational
Center of Kazan State University Basic Research and
Higher Education (BRHE) Russian American
Collaborative Program, grant no. REC-007].
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powder, mp 43 45 C, yield 58%,
37 ppm.
P
Synthesis of O,O-dibutyl ( -aminomethyl)thio-
phosphonates (general procedure). O,O-Dibutyl thio-
phosphite, 50 mmol, was mixed with equimolar amo-
unts of Paraform and secondary amine, and 35 ml of
anhydrous toluene and about 100 mg of p-toluenesul-
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 6 2004
Zakharov
