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GAZIZOV et al.
1
3
2
[5]). H NMR spectrum, δ, ppm: 1.20 s (18H, CMe3),
19.2 Hz), 4.08 d.d (1H, CH, JPH 19.2, JPH 9.2 Hz),
5.19 br.s (1Н, ОН), 7.04 s (2Н, С6Н2). 31P NMR
1.2 t (6Н, СН2Me, 3JHH 7.5 Hz), 1.7 d.q (4H, CH2Me,3JНH
2
3
7.5, JРH 22.5 Hz), 5.09 br.s (1Н, ОН), 5.90 d (1Н,
spectrum, δР, ppm: 49.91 d (Р1, JPР 32.4 Hz), 95.86 d
2
СНР, JРH 22.5 Hz), 6.65 s and 8.30 s (2H, C6Н2).
Found Р, %: 9.30, 9.60. C19H31O2P. Calculated Р, %:
(Р2, 3JPР 32.4 Hz). Found Р, %: 11.50, 12.05. C23H42O4P2S2.
Calculated Р, %: 12.20.
9.62.
O,O-Diisopropyldithiophosphato(4-hydroxy-3,5-
di-tert-butylphenyl)methanediethylphosphineoxide
(IIId) was prepared similarly from 0.97 g (0.003 mol)
of quinone Ib and 0.67 g (0.0031 mol) of O,O-diiso-
propyldithiophosphoric acid IIb. Yield 1.36 g (84%),
O,O-Diethyldithiophosphato(4-hydroxy-3,5-di-
tert-butylphenyl)methanediphenylphosphine oxide
(IIIa). A mixture of 0.63 g (0.0015 mol) of quinone Ia
and 0.29 g (0.0016 mol) of O,O-diethyldithiophos-
phoric acid IIa in 12 mL of benzene was allowed to
stand at room temperature during 24 h. After removal
of the solvent, the residue was treated with hexane and
recrystallized. Yield 0.86 g (89%), mp 165–166°C
1
mp 142–145°C (isooctane). H NMR spectrum, δ,
3
ppm: 0.93 d and 1.25 d (6Н, OCHMe2, JHH 6.4 Hz),
3
0.96 d and 1.35 d (6H, OCHMe, JHH 6.0 Hz), 1.01 t
3
and 1.24 t (6Н, РCH2Ме, JHH 7.6 Hz), 1.43 s (18Н,
1
(toluene–heptane). H NMR spectrum, δ, ppm: 0.80 t
and 0.92 t (6H, OCH2Me, JHH 7.2 Hz), 1.17 s (18H,
CMe3); 3.29 d.q, 3.41 d.q, 3.52 d.q and 3.73 d.q (4H,
СМе3), 1.53–2.14 m (4Н, РCH2), 4.28 septet and 4.78
septet (2H, ОCHMe2, 3JHH 6.4 Hz), 4.78 d.d (1Н, РСН,
3JРH 20.0, 2JРH 9.2 Hz), 5.10 br.s (1H, OH), 7.29 s (2Н,
3
3
3
OCH2Me, JHH 7.2, JPH 14.4 Hz), 4.74 d.d (1H, CH,
3JPH 19.6, 2JPH 9.2 Hz), 4.91 br.s (1Н, ОН), 6.86 s (2Н,
С6Н2), 7.06–7.83 m (10Н, Ph). 31P NMR spectrum, δР,
3
С6Н2). 31P NMR spectrum, δР, ppm: 50.65 d (Р1, JPР
3
36.5 Hz), 94.61 d (Р2, JPР 36.5 Hz). Found Р, %:
10.90, 11.18. C25H46O4P2S2. Calculated Р, %: P 9.81.
ppm: 28. 97 d (Р1, JPР 38.07 Hz), 96.38 d (Р2, JPР
38.07 Hz). Found Р, %: 10.24, 10.65. С31Н42O4P2S2.
Calculated Р, %: 10.26.
3
3
ACKNOWLEDGMENTS
This work was financially supported by the
Government of the Republic of Tatarstan, the Russian
Foundation for Basic Research (grant no. 13-03-
97098) and the Ministry of Education and Science of
Russian Federation in the frame of the basic part of the
governmental task (no. 2014/56).
O,O-Diisopropyldithiophosphato(4-hydroxy-3,5-
di-tert-butylphenyl)methanediphenylphosphine
oxide (IIIb) was prepared similarly from 0.42 g
(0.001 mol) of quinone Ia and 0.23 g (0.0011 mol) of
O,O-diisopropyldithiophosphoric acid IIb. Yield
0.52 g (83%), mp 169–173°C (toluene–heptane). 1H NMR
spectrum, δ, ppm: 0.68 d, 0.88 d, 0.93 d and 1.17 d
3
REFERENCES
(12Н, Me2СНО, JHH 6.2 Hz), 1.25 s (18Н, СMe3),
4.29 d. septets, 4.02 d. septets (2H, Me2CHО, 3JHH 6.2,
3JPH 12.1 Hz), 4.97 d.d. d (1H, CH, 3JPH 20.6, 2JPH 8.8,
4JHH 4.0 Hz), 4.81 br.s (1H, ОН), 7.14 d (2Н, С6Н2,
4JHH 4.0 Hz), 7.21–7.95 m (10Н, Ph). 31P NMR
1. Gross, H., Ozegowski, S., and Сostisella, В.,
Phosphorus, Sulfur, Silicon, Relat. Elem., 1990, vol. 47,
p. 7.
3
spectrum, δР, ppm: 30. 51 d (Р1, JPР 42.12 Hz), 95.45
2. Сostisella, В., Keitel, I., and Ozegowski, S.,
Phosphorus, Sulfur, Silicon, Relat. Elem., 1993, vol. 84,
p. 115.
3
d (Р2, JPР 42.12 Hz). Found Р, %: 9.45, 9.47.
C33H46O4P2S2. Calculated Р, %: 9.81.
3. Gazizov, M.B., Ismagilov, R.K., Karimova, R.F.,
Shamsutdinova, L.P., Burangulova, R.N., and Ivano-
va, S.Yu., Russ. J. Gen. Chem., 2014, vol. 84, no. 4,
p. 654. DOI: 10.1134/S1070363214040094.
O,O-Diethyldithiophosphato(4-hydroxy-3,5-di-
tert-butylphenyl)methanediethylphosphine oxide
(IIIc) was prepared similarly from 0.97 g (0.003 mol)
of quinone Ib and 0.586 g (0.0031 mol) of O,O-
diethyldithiophosphoric acid IIa. Yield 1.32 g (87%),
4. Gazizov, M.B., Ismagilov, R.K., Karimova, R.F.,
Shamsutdinova, L.P., Tarakanova, A.L., and Karimo-
va, A.A., Vestn. Kazansk. Tekhnol. Univ., 2014, no. 5,
p. 29.
1
mp 117–118°C (isooctane). H NMR spectrum, δ,
3
ppm: 0.75 t and 0.99 t (6H, OCH2Me, JHH 7.2 Hz),
0.78–0.82 m and 1.01–1.06 m (6Н, РСН2Me), 1.57–
1.83 m (4Н, РСН2), 1.28 s (18Н, СMe3); 3.92 d.q, 3.71
d.q, 3.50 d.q and 3.39 d.q (4H, OCH2Me, 3JHH 7.2, 3JPH
5. Ismagilov, R.K., Moskva, V.V., Arkhipov, V.P.,
Ivantsov, A.E., and Kopylov, L.Yu., Zh. Obshch. Khim.,
1991, vol. 61, no. 2, p. 387.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 11 2014