Optically active aryldithiophosphonic acids and their salts based on L-(-)-menthol and D-(+)-menthol

Full text of DOI:10.1134/S1070428009020260

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 2, pp. 300−301. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.V. Sofronov, L.A. Al’metkina, E.N. Nikitin, I.S. Nizamov, R.A. Cherkasov, 2009, published in Zhurnal Organicheskoi
Khimii, 2010, Vol. 46, No. 2, pp. 304−305.
SHORT
COMMUNICATIONS
Optically Active Aryldithiophosphonic Acids
and Their Salts Based on L-(−)-Menthol and D-(+)-Menthol
A. V. Sofronova, L. A. Al’metkinaa, E. N. Nikitinc, I. S. Nizamova,b,c, and R.A. Cherkasova
aKazan State University, Kazan, 420008 Russia
e-mail: Ilyas.Nizamov@ksu.ru, nizamov@iopc.knc.ru
bArbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Science, Kazan, Russia
c Tatar State Humanitarian Pedagogical University, Kazan, Russia
Received July 23, 2009
DOI: 10.1134/S1070428009020260
Thioacids of tetracoordinate phosphorus and their
derivatives serve as basic compounds for production of
most isecticides, acaricides, fungicides etc. [1, 2].
A special interest among them attract biologically active
organothiophosphorus compounds obtained in the
reactions of phosphorus sulfides with individual enantio-
mers of natural compounds, e.g., terpenes. Recently the
determination of an enantiomeric and diastereomeric
excess of chiral alcohols was performed with the use of
tetraphosphorus decasulfide [3, 4]. In this connection we
suggested that at bringing into the reaction of optically
pure terpenols of L- and D-series and other phosphorus
sulfides, for instance, 1,3,2,4-dithiadiphosphethene 2,4-
disulfides [5] optically active thioacids of tetracoordinate
phosphorus may be obtained with a selective physiological
activity (eutomers).
In this study we selected as chiral substrates for
thiophosphorylation L-(–)- and D-(+)-menthol. We
established that 2,4-bis-(3,5-di-tert-butyl-4-hydroxy-
phenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide (I)
effected the thiophosphorylation of L-(–)-menthol (IIa)
at 50°C within 1 h in chloroform to furnish O-L-(–)-
menthyl-3,5-di-tert-butyl-4-hydroxyphenyl-
dithiophosphonic acid (IIIa). Acid IIIa was optically
active, [α]D22 –33.2° (c 1.0, C6H6), in conformity with the
sign of the rotation angle of the plane-polarized light of
alcohol IIa [α]D23 –48° (c 10, EtOH) [6]. The isomeric
O-D-(+)-menthyl-3,5-di-tert-butyl-4-hydroxy-
phenyldithiophosphonic acid (IIIb) was cleanly produced
by heating a mixture of D-(+)-menthol (IIb) and
dithiadiphosphethane disulfide I under similar conditions.
Acid IIIb also conserved the sign of the angle of the
1/2
S
SH
OH
O P
Ar
IIa
S
S
IIIa
Ar
P
P Ar
S
Ph
S
H2N
H
C
I
+
_
S
Me
S
Ph
S
H2N
SH
Ar
IV
C
1/2
O P
IIIb
300
O P
H
Me
OH
Ar
.
Ar = HO
IIb
V

OPTICALLY ACTIVE ARYLDITHIOPHOSPHONIC ACIDS AND THEIR SALTS
301
optical rotation [α]D22 +32.4° (C 1.0, C6H6), of alcohol
IIb [α]D23 +48° (c 10, EtOH) [6]. The parameters of IR
spectra, 31P and 1H NMR, and mass spectra of isomeric
acids IIIa and IIIb are identical. L-(–)-α-Methylbenzyl-
ammonium salt of O-L-(–)-menthyl-3,5-di-tert-butyl-4-
hydroxy-phenyl-dithiophosphonic acid (V) obtained by
treating acid IIIa with L-(–)-α-methylbenzylamine (IV)
retained the optical activity, [α]D22 –39.2° (c 1.0, C6H6).
and kept for 12 h at 20°C. The solution was evaporated
at a reduced pressure (0.5 mm Hg) for 1 h at 40°C and
in a vacuum (0.02 mm Hg) for 1 h at 40°C. Solid salt V
was obtained. Yield 0.9 g (90%). IR spectrum (mull in
mineral oil), ν, cm–1: 3639 (O–H), 3365 (NH3 ), 1582
+
(C=C, Ar), 1458 [δas(CH3)], 1377 [δs(CH3)], 981 [(P)O–
1
C], 670 (P=S), 539 (P–S). H NMR spectrum, δ, ppm:
3
0.32 d (3H, CH3CHN, JHH 6.7 Hz), δ1 0.68 d [6H,
3
(CH3)2CH, JHH 7.0 Hz] and δ2 0.72 d [6H, (CH3)2CH,
O-L-(–)-Menthyl-3,5-di-tert-butyl-4-hydroxy-
phenyl-dithiophosphonic acid (IIIa). To a solution of
1.0 g (6.4 mmol) of alcohol IIa in 50 ml of anhydrous
chloroform at 20°C in a flow of dry argon was added
under stirring by portions 2.0 g (3.3 mmol) of reagent I.
The mixture was heated at stirring for 1 h at 50°C and
then it was filtered. The filtrate was evaporated for 1 h
at a reduced pressure (0.5 mm Hg) and for 1 h in a
vacuum (0.02 mm Hg) at 40°C. We obtained as a residue
2.6 g (87%) of acid IIIa. IR spectrum, ν, cm–1: 3629
(O–H,Ar), 2957, 2940, 2871 [νas,s(CH3), νas,s(CH2)], 2550
(S–H, free), 2400 (S–H, bound), 1550 (C=C, Ar), 1455,
1430 [δas(CH3)], 1369 [δs(CH3)], 985 (O–C), 662 (P=S),
511 (P–S). 1H NMR spectrum, δ, ppm: 0.83 d, 0.88 d
(3H, CH3CH, 3JHH 6.6 Hz), 0.94 d, 0.95 d [6H, (CH3)2CH,
3JHH 7.0 Hz), 1.49 s [18H, (CH3)3C, Ar], 1.13 m (2H,
CH3CHCH2CH2 cycle), 2.18 m (2H, POCHCHCH2
cycle), 2.50 m (2H, POCHCH2 cycle), 3.44 m (1H,
POCHCHcycle), 4.70 m (1H, POCH cycle), 7.83 d (2H,
2,6-C6H2P, 3JPH 16.1 Hz). 31P NMR spectrum (CHCl3),
δ, ppm: 86.1. Mass spec-trum, m/z (Irel, %): 456.3 [M]+·.
Found, %: C 62.92; H 9.06; P 6.80; S 14.37.
C24H41O2PS2. Calculated, %: C 63.12; H 9.05; P 6.78; S
14.04. M 456.7.
3JHH 6.7 Hz], 0.76–0.94 m (CH), 1.87 m (2H
3
CH3CHCH2CH2 cycle, JHH 7.0 Hz), 2.13 m (2H,
3
POCHCHCH2 cycle), 3.95 d.d.t (1H, POCH, JHH 6.3,
3
3JPH 13.0 Hz), 4.08 q (1H, NCH, JHH 6.7 Hz), 5.35 m
(1H, HOCAr), 7.18 narrow m (5H, C6H5), 8.04 δ (2H,
3
2,6-C6H2P, JHH 14.9 Hz). 31P NMR spectrum (C6H6),
δ, ppm: 103.0. Mass spectrum (Electron impact), m/z
(Irel, %): 578.3 [Μ]+·. Found, %: C 66.86; H 9.47; N 2.12;
P 4.97; S 11.50. C32H52NO2PS2. Calculated, %: C 66.51;
H 9.07; N 2.42; P 5.36; S 11.10.
IR spectra were recorded on an infrared Fourier
1
spectrometer Bruker Vector 22. H NMR spectra were
registered on a spectrometer Avance-600 (600 ΜHz) in
CDCl3, 31P NMR spectra were taken on an instrument
Bruker CXP-100 (36.5 ΜHz) with respect to an external
reference (85% H3PO4). Mass spectra were measured
on a mass spectrometer TRACE MS Finnigan MAT
22
(70 eV, direct admission). The [α]D value was
determined on a polarimeter Perkin Elmer instruments
341 (λ 589 nm, sodium-halogen lamp).
REFERENCES
1. Mel’nikov, N.N., Pestitsidy (khimiya tekhnologiya i
primenenie) (Pesticides: Chemistry, Technology, and
Application), Moscow: Khimiya, 1987, p. 712.
2. Mel’nikov, N.N., Novozhilov, K.V., and Belan, S.R., Pestitsidy
i regulyatory rosta rastenii (Pesticides and Plant Growth
Regulator), Moscow: Khimiya, 1995, p. 576.
3. Al’fonsov, V.A., Garifzyanova, G.G., Dimukhametov, M.N.,
and Bredikhin,A.A., Zh. Obshch. Khim., 1998, vol. 68, p. 517.
4. Feringa, B.L., Chem. Commun., 1987, p. 695.
5. Maier, L., Topics in Phosphorus Chemistry, Grayson, M.
and Griffith, E.J., NewYork: J.Wiley, 1980, vol. 10, p. 129.
6. Aldrich Catalog Handbook of Fine Chemicals, Milwaukee,
USA, 1994−1995, 1016, p.
O-D-(+)-Menthyl ester of 3,5-di-tert-butyl-4-
hydroxy-phenyl-dithiophosphonic acid (IIIb) was
analogously obtained from 1.0 g (64 mmol) of alcohol
IIb and 2.0 g (3.3 mmol) of reagent I. Yield 2.9 g (97%).
O-L-(–)-Menthyl-3,5-di-tert-butyl-4-hydroxy-
phenyldithiophosphonic acid L-(–)-α-methyl-
benzylammonium salt (V). To a solution of 0.8 g (1.8
mmol) of acid IIIa in 10 ml of anhydrous benzene at
20°C in a flow of dry argon under stirring was added
dropwise a solution of 0.2 g (1.7 mmol) of amine IV in 10
ml of benzene. The mixture was stirred for 1 h at 20°C
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 2 2010