1552
KORNILOV, ROEVA
cannot be prepared in this way for further use in the
synthesis of macrocycles.
(B). 1Н NMR spectrum, δ,ppm: 0.98 t (12Н, СН3, 3JHH
=
3
7.1 Hz), 3.30 m (8Н, СН2, JРH = 10.4 Hz), 7.34 m
(2H, p-CH, Ph), 7.50 d (2Н, о-СН, pyrocatechol, 3JHH
=
All syntheses involving P(III) compounds were
performed under dry argon. Thin-layer chromato-
graphy was performed using Silufol plates in 3 : 1
hexane–dioxane (А) or 5 : 1 chloroform–ethanol
systems (B); the spots were visualized in UV light or
by calcination at 200–250°C. Column chromatography
was performed on silica gel L 100/250.
5.8 Hz), 7.52 m (2Н, m-СН, pyrocatechol), 7.78 m
(4Н, о-СН, Ph, 3JРH = 12.60, 3JHH = 8 Hz), 7.96 m (4Н,
m-СН, Ph). 31Р NMR spectrum: δР 9.27 ppm. Mass
spectrum, m/z: 501.19 [M + H]+. Found Р, %: 12.43.
С26Н34N2O4P2. Calculated Р, %: 12.40.
The 31Р NMR spectra were measured on a Bruker
WP-80SY spectrometer at 32.4 МHz against 85%
O,O'-(Benzene-1,2-diyl) bis(N,N-diethylphenyl-
phosphonothioamidate) (5). Phenylphosphonous amide
2, 1.52 g (6 mmol), was added with stirring to 0.33 g
(3 mmol) of pyrocatechol 1. The reaction mixture was
heated at 100°С in a vacuum (10 mmHg) for 4 h and
then let to cool down to obtain a light yellow thick
thermoplastic glassy material, the 31Р NMR spectrum
of which showed two major (179.09 and 132.89 ppm)
and a few minor signals (0–35 ppm) characteristic of
oxidation products. The material was then dissolved
under heating in 20 mL of benzene, and 0.19 g
(6 mmol) of crystalline sulfur was added to it. The
mixture was stirred until sulfur dissolved completely
and left to stand for 24 h. The precipitate that formed
was separated. The 31Р NMR spectrum of the filtrate
showed a major signal at 77.26 ppm and a few minor
signals in the range 0–16 ppm (intensity ratio 1 : 0.27).
Thione phosphonate 5 was isolated by column
chromatography, eluent benzene, and then dried for 2 h
at 50°С in a vacuum (10 mmHg). Compound 5 was a
light yellow solid paste liquefied at 55°С. Yield 0.38 g
1
phosphoric acid. The Н NMR spectra were obtained
on a Bruker AM-400 spectrometer at 400 МHz for
CDCl3 solutions. The MALDI mass spectra were
measured on a Bruker Daltonics Autoflex II MALDI-
ToF instrument with a nitrogen laser source (λ 337 nm),
operated in the positive ion mode.
CONFLICT OF INTERESTS
No conflict of interest was declared by the authors.
REFERENCES
1. Soldatova, I.A., Cand. Sci. (Chem.) Dissertation,
Moscow, 1990.
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on Phosphorus Chemistry, Kazan, 2016, p. 318.
1
(24%), Rf 0.70 (А). Н NMR spectrum, δ, ppm: 0.99 t
3
3
(12Н, СН3, JHH = 7.1 Hz), 3.32 m (8Н, СН2, JРH
=
10.4 Hz), 7.36 m (2H, p-CH, Ph), 7.48 d (2Н, о-СН,
3
pyrocatechol, JHH = 6.0 Hz), 7.52 m (2Н, m-СН,
pyrocatechol), 7.78 m (4Н, о-СН, Ph, 3JРH = 12.0,3JHH
=
8.0 Hz), 7.96 m (4Н, m-СН, Ph). 31Р NMR spectrum:
δР 77.26 ppm. Mass spectrum, m/z: 533.15 [M + H]+.
Found Р, %: 11.64. С26Н34N2O2P2S2. Calculated Р, %:
11.65.
O,O'-(Benzene-1,2-diyl) bis(N,N-diethylphenyl-
phosphonamidate) (6). The reaction mixture after the
reaction of 3 mmol of pyrocatechol 1 and 6 mmol of
phosphonous amide 4 was dissolved in ethyl acetate
and stirred in air for 4 h. The solvent was removed in a
vacuum. The residue was heated in hexane under
reflux, and the undissolved substances were separated.
The filtrate was let to cool down, and the resulting
thick material was dried in a vacuum for 2 h at 50°С in
a vacuum (10 mmHg) to obtain compound 8 as a light
yellow powder, mp 50°С. Yield 0.42 g (27%), Rf 0.80
8. Nifantyev, E.E., Slitikov, P.V., and Rasadkina, E.N.,
Russ. Chem. Rev., 2007, vol. 76, p. 327. doi 10.1070/
RC2007v076n04ABEH003667
9. Kornilov, K.N., Cand. Sci. (Chem.) Dissertation,
Moscow, 2008.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 7 2018