SYNTHESIS OF OPTICALLY ACTIVE O,O-DI-L-(–)-
1723
S
S
+
Ph
Ph
H2N
H2N
H
*
*
C
PSH +
O
C
PS
O
H
Me
Me
2
2
IIIа
V
IV
phosphorus sulfide I at 20°С in the dry argon flow
under stirring. This mixture was heated at 50°С for 2 h
under stirring. After cooling the mixture was filtered
and concentrated for 1 h (0.5 mm Hg) at 40°С and for
1 h (0.02 mm Hg) at 40°С. Yield 11.5 g (88%). IR
spectrum, ν, cm–1: 2406 w.br [ν(S–H)]; 2955 s, 2924 s,
2854 s [νas,s(СН3), νas,s(CH2)]; 1458 s [δas(CH3)]; 1377
m [δs(CH3)]; 1023 m, 985 m, 963 m.br [ν(P–O–C)],
νas,s(CH2), СН]; 1589 m, 1495 m [ν(С=С, Ar)]; 1453 s
[δas(CH3)]; 1389 m, 1370 m [δs(СН3)2Cgem]; 1021 s
[ν(Р–О–С)]; 978 s.br [ν(О–С)]; 670 s [ν(P=S)]; 576 m
1
[ν(P–S)]. Н NMR spectrum, δ, ppm: 0.79 d, 0.80 d,
3
0.81 d and 0.84 d (6Н×2, СН3СН-cycl., JНН 7.0 Hz);
0.88 d, 0.89 d, 0.895 d and 0.90 d [12Н, (СН3)2СН,
3JНН 7.0 Hz]; 0.98–1.11 br.s (CH); 1.27 m (СН); 1.40
3
m (CH); 1.50 d (3H, СН3СНN, JНН 6.7 Hz); 1.63 m
1
3
[ν(O–C)]; 675 m [ν(P=S)]; 548 w [ν(P–S)]. Н NMR
(CH2); 1.94 m (CH); 2.17 m and 2.34 m (СН2, JНН
spectrum, δ, ppm: 0.83 d and 0.86 d (3Н×2, СН3СН,
3JНН 8.8 Hz); 0.94 d and 0.95 d (6Н×2, (СН3)2СН, 3JНН
6.6 Hz); 1.15 m [1H×2, (CH3)2CH–CH); 1.43 m
(1Н×2, СН3СН cycl.); 1.69 m (2Н×2, СН3СН·
СН2СН2); 1.99 d (1Н×2, РОСНСНH-а, 3JНН 11.7 Hz);
2.09–2.21 m (2Н×2, РОСНСНСН2); 2.38 d (1Н×2,
7.0 Hz); 3.40 d.d.t (1Н×2, РОСНСН-cycl., 3JНН 6.0 Hz);
4.02 m (1Н, NCH); 4.20–4.30 m (1Н×2, РОСН-cycl.,
3JНН 7.0 Hz); 7.26–7.38 m (5Н, С6Н5). 31Р NMR
spectrum (С6Н6), δР, ppm: 106.6. Mass spectrum (EI),
m/z: 527 [M]+. Found, %: С 63.82; Н 9.43; N 2.99; Р
5.68; S 12.43. С28Н50NО2Р. Calculated, %: С 63.72; Н
9.55; N 2.65; Р 5.87; S 12.15. М 527.8
3
РОСНСНH-е, JНН 11.7 Hz); 3.44 d.t (1Н×2,
3
РОСНСH-cycl., JНН 6.6 Hz); 4.46 d.d.t (1Н×2,
The IR spectra were recorded on a Bruker Vector
22 IR Fourier-spectrometer (KBr). The 1Н NMR
spectra were taken on an Avance-600 spectrometer
(600 MHz) in CDCl3; the 31Р NMR spectra, on a
Bruker CXP-100 spectrometer (36.5 MHz) relative to
external reference (85% Н3РО4) in СHCl3. The mass
spectra were registered on a TRACE MS Finnigan
MAT mass-spectrometer (70 eV).
3
3
РОСH-cycl., JНН 6.6 Hz, JРH 11.0 Hz). 31Р NMR
spec-trum, δР, ppm: 81.9. Mass spectrum (EI), m/z:
406 [M]+.. Found, %: С 59.36; H 9.76; P 7.48; S 15.63.
С20Н39О2РS2. Calculated, %: C 59.09; H 9.67; P 7.62;
S 15.77. Mr 406.6.
О,О-Di-D-(+)-menthyldithiophosphoric acid (IIIb).
Yield 88%. Found, %: С 59.36; Н 9.56; Р 7.25; S
15.48. С20Н39О2PS2. Calculated, %: С 59.07; Н 9.67; Р
7.62; S 15.77.
REFERENCES
L-(–)-α-Methylbenzylammonium salt of О,О-di-
L-(–)-menthyldithiophosphoric acid (V). To a solu-
tion of 3.2 g of acid IIIа in 10 ml of anhydrous
benzene was added dropwise a solution of 0.95 g of
amine IV in 10 ml of benzene at 20°С in the dry argon
flow under stirring. This mixture was stirred for 1 h at
20°С, then kept for 12 h at 20°С and concentrated for
1 h under vacuum (0.5 mm Hg) at 40°С and for 1 h
(0.02 mm Hg) at 40°С. Yield 2.9 g (70%). IR
spectrum, ν, cm–1: 3345 w.br [νfree(NH3+)]; 3273 w
[νbonded(NH3+)]; 2954 s, 2974 s, 2868 s [νas,s(СН3),
1. Nizamov, I.S., Sofronov, A.V., Nizamov, I.D.,
Cherkasov, R.A., and Nikitina, L.E., Zh. Obshch. Khim.,
2007, vol. 43, no. 4, p. 621.
2. Al’fonsov, V.A., Garifzyanova, G.G., Dimukhame-
tov, M.N., and Bredikhin, А.А., Zh. Obshch. Khim.,
1998, vol. 68, no. 3, p. 517.
3. Feringa, B.L.J., Chem. Soc., Chem. Commun., 1987,
no. 9, p. 695.
4. Aldrich. Catalog Handbook of Fine Chemicals,
Milwaukee, USA, 1994–1995, p. 933,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010