Thiophosphorylation of thymol with phosphorus sulfides

Full text of DOI:10.1134/S1070428013010247

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 1, pp. 145–146. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © I.S. Nizamov, G.T. Gabdullina, L.A. Al’metkina, R.R. Shamilov, R.A. Cherkasov, 2013, published in Zhurnal Organicheskoi Khimii,
2013, Vol. 49, No. 1, pp. 149–150.
SHORT
COMMUNICATIONS
Thiophosphorylation of Thymol with Phosphorus Sulfides
I. S. Nizamova, b, G. T. Gabdullinaa, L. A. Al’metkinaa, R. R. Shamilova, and R. A. Cherkasova
a Kazan Federal University, ul. Kremlevskaya 18, Kazan, 420008 Tatarstan, Russia
e-mail: isnizamov@mail.ru
b Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
Received May 30, 2012
DOI: 10.1134/S1070428013010247
In continuation of our studies on thiophosphoryla-
tion of alcohols [1], the present communication reports
on the reaction of one of the most accessible [2]
aromatic monoterpenoids, thymol (I), with tetraphos-
phorus decasulfide (II) and 2,4-bis(3,5-di-tert-butyl-
4-hydroxyphenyl)-1,3,2λ5,4λ5-dithiadiphosphetane
2,4-disulfide (V). The reaction of thymol (I) with sul-
fide II at 50°C in 2 h afforded O,O-bis(2-isopropyl-5-
methylphenyl) hydrogen dithiophosphate (III) in good
yield (Scheme 1). Compound III displayed in the
31P NMR spectrum a singlet at δP 76.5 ppm which ap-
peared in a stronger field relative to the corresponding
signal of an aliphatic analog of III, O,O-bis-
[(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl] hydro-
gen dithiophosphate (δP 81.9 ppm), recently prepared
by reaction of II with L-(–)-menthol [1]. Treatment of
acid ester III with gaseous ammonia produced am-
monium salt IV; the phosphorus nuclei in IV resonated
at δP 105.8 ppm, i.e., in the region typical of dithio-
phosphoric acid salts [3].
Dithiophosphorylation of thymol with dithiadiphos-
phetane disulfide V (50°C, 1 h) gave O-3,5-di-tert-
butyl-4-hydroxyphenyl hydrogen dithiophosphonate
VI (Scheme 2).
Scheme 2.
Me
Ar
S
S
S
HS
O
S
2I
+
2
P
P
P
Ar
S
Ar
Me
Me
VI
V
t-Bu
Ar =
.
HO
Scheme 1.
Bu-t
7Me
5
O,O-Bis(2-isopropyl-5-methylphenyl) hydrogen
dithiophosphate (III). Tetraphosphorus decasulfide
(II), 3.3 g (7.4 mmol), was added in portions at 20°C
under stirring in a stream of dry argon to a solution of
9.0 g (6.0 mmol) of thymol (I) in 20 ml of anhydrous
benzene. The mixture was stirred for 2 h at 50°C,
cooled, and filtered, and the filtrate was evaporated at
40°C under reduced pressure (for 1 h at 0.5 mm and
for 1 h at 0.02 mm). Yield 9.3 g (79%). IR spectrum, ν,
cm–1: 3035 (C–Harom), 2959, 2928, 2869 [νas,s(CH3),
ν(CH)], 2487 (S–H, unassoc.), 2345, 2323 (S–H,
assoc.), 1622, 1585, 1517 (C=Carom), 1459 [δas(CH3)],
1386, 1361 [δsC(CH3)2], 1091, 1050 (P–O), 944
(OC–C), 739 [νas, s(PO2)], 692 (P=S), 526 (P–S).
6
1
4
3
8
+
P4S10
OH
2
8
9
Me
10
Me
I
II
Me
Me
HS
S
4
P
–2H2S
O
O
Me
Me
Me
Me
III
145

NIZAMOV et al.
146
1H NMR spectrum, δ, ppm (J, Hz): 1.26 d [12H,
1.24 d [6H, (CH3)2CH, 3JHH = 7.2], 1.43 s (18H, t-Bu),
3
3
2.27 s (3H, CH3), 3.14 sept [(CH3)CH, JHH = 6.8];
(CH3)2CH, JHH = 7.0], 2.29 s (6H, CH3), 3.18 sept
3
3
6.58 s (1H, 6-H), 6.73 d (1H, 4-H, JHH = 7.9); 7.08 d
[2H, (CH3)2CH, JHH = 7.0], 6.60 s (2H, 6-H), 6.75 d
3
3
3
3
(1H, 3-H, JHH = 7.9), 7.83 d (2H, Harom, JPH = 15.7).
31P NMR spectrum (C6H6): δP 86.0 ppm. Found, %:
C 64.00; H 7.81; P 6.68; S 14.17. C24H35O2PS2. Cal-
culated, %: C 63.97; H 7.83; P 6.87; S 14.23.
(2H, 4-H, JHH = 7.6), 7.09 (2H, 3-H, JHH = 7.6).
Found, %: C 60.68; H 6.91; P 7.33; S 16.11.
C20H27O2PS2. Calculated, %: C 60.89; H 6.90; P 7.85;
S 16.26.
Ammonium O,O-bis(2-isopropyl-5-methyl-
phenyl) dithiophosphate (IV). A suspension of 8.1 g
(53.9 mmol) of thymol (I) and 3.0 g (6.8 mmol) of
sulfide II in 30 ml of anhydrous benzene was stirred
for 1 h at 50°C. The mixture was cooled to ~20°C and
filtered, and gaseous ammonia was bubbled through
the filtrate at ~20°C over a period of 1 h. The mixture
was stirred for 12 h at ~20°C and evaporated at 40°C
under reduced pressure (1 h at 0.5 mm and 1 h at
0.02 mm). Yield 6.1 g (55%), mp 50–51°C. Found, %:
C 58. 66; H 2. 24; N 3. 01; P 7. 11; S 15. 44.
C20H30NO2PS2. Calculated, %: C 58.37; H 7.35;
N 3.40; P 7.53; S 15.58.
The IR spectra were recorded on a Bruker Vector
22 spectrometer with Fourier transform from samples
prepared as thin films, suspensions in mineral oil, or
1
KBr pellets. The H NMR spectra were measured on
a Bruker Avance-600 spectrometer (600 MHz) from
solutions in CDCl3; the chemical shifts were deter-
mined relative to the residual proton signal of the
solvent. The 31P NMR spectra were obtained on
a Bruker Avance-400 instrument at 161.98 MHz using
benzene as solvent and 85% phosphoric acid as ex-
ternal standard.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 11-03-00264a).
O-(2-Isopropyl-5-methylphenyl) hydrogen
(3,5-di-tert-butyl-4-hydroxyphenyl)dithiophospho-
nate (VI). Disulfide V, 1.1 g (1.8 mmol), was added in
portions at 20°C under stirring in a stream of dry argon
to a solution of 0.6 g (4.0 mmol) of thymol (I) in 20 ml
of anhydrous benzene. The mixture was stirred for 1 h
at 50°C, cooled to 20°C, and filtered. The filtrate was
evaporated at 40°C under reduced pressure (1 h at
0.5 mm and 1 h at 0.02 mm). Yield 2.4 g (72%). IR
spectrum, ν, cm–1: 3620 (O–H), 3034 (C–Harom), 2963,
2872 [νas,s(CH3), ν(CH)], 2535 (S–H, unassoc.), 2345
(S–H, assoc.), 1579, 1479 (C=Carom), 1363, 1323
[δsC(CH3)2], 1086 [PO–C], 963 (OC–C), 678, 662
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3. Crutchfield, M.M., Dungan, C.H., Letcher, J.H.,
Mark, V., and Van Wazer, J.R., P31 Nuclear Magnetic
Resonance (Topics in Phosphorus Chemistry, vol. 5),
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1
(P=S), 502 (P–S). H NMR spectrum, δ, ppm (J, Hz):
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 1 2013