chemical ionization (CI) mass spectra were recorded on a
double focussing MAT 8220 instrument (Finnigan AT,
Bremen). Ammonia served as the reagent gas for CI experi-
ments. The high resolution EI data were obtained by peak
matching at a resolution of approximately 10.000 (10% valley
deÐnition). The metastable ion spectra were recorded using
linked scans (B/E constant).
18O-[Methoxy(phenoxy)phosphoryl]methyl p-tolyl sulfoxide
(18O-10). To a solution of sulfoxide 18O-8 (0.038 g, 0.1 mmol)
in dioxane (3 mL), a solution of potassium hydroxide (0.02 g,
0.4 mmol) in water (0.5 mL) was added. The reaction mixture
was stirred for 1 h at room temperature, acidiÐed with tri-
Ñuoroacetic acid and extracted with chloroform (3 ] 10 mL).
The chloroform extracts were dried over MgSO and concen-
4
trated to a†ord phosphonic acid 9 [31P NMR (CDCl ): 6.5
3
TLC was carried out on silica gel plates (Merck F ) and
254
silica gel 60 (70È230 ASTM) was used for column chromatog-
ppm]. The crude acid 9, prepared as above, was dissolved in
raphy.
diethyl ether (5 mL) and an excess of diazomethane dissolved
in diethyl ether (5 mL) was added. After 15 min, the ether was
removed, a†ording the crude sulfoxide 18O-10 (mixture of
diastereoisomers), which was puriÐed by thin layer chroma-
tography (benzeneÈacetone, 3 : 1); 0.28 g, 86% yield. 31P
Syntheses
[Methoxy(phenoxy)phosphoryl]methyl p-tolyl sulÐde (11).
To a solution of sulÐde 12 (0.26 g, 0.7 mmol) in dioxane (10
mL), potassium hydroxide (0.15 g, 2.7 mmol) in water (1 mL)
was added. The reaction mixture was stirred at room tem-
perature for 1 h and then acidiÐed and extracted with chloro-
NMR (CDCl ) d: 15.0 and 14.6 (1.2 : 1).
3
Alkaline hydrolysis of sulfoxide 8. To a solution of sulfoxide
(0.06 g, 0.15 mmol) in dioxane (1 mL), a solution of potassium
hydroxide (0.04 g, 0.65 mmol) in 18O-water (1 mL) was added.
The reaction mixture was stirred for 1 h at room temperature.
Then the reaction solution was acidiÐed with triÑuoroacetic
acid and extracted with chloroform (3 ] 10 mL). The organic
form (3 ] 10 mL). The extract was dried over MgSO and
4
concentrated to give a mixture of the corresponding phos-
phonic acid 13 (d \ 23.3) and phenol. The crude acid 13 was
p
dissolved in diethyl ether (10 mL) and treated with an excess
of an ethereal solution of diazomethane. After 15 min, the
solvent was removed under vacuum and the residue was puri-
Ðed by thin layer chromatography (benzeneÈacetone, 4 : 1)
a†ording sulÐde 11 as an oil (0.19 g, 88% yield). 1H NMR
(CDCl ) d: 2.33 (3H, s, CH Ph); 3.30 (2H, d, J \ 13.6, CH P);
extracts were dried over MgSO and evaporated to a†ord
4
phosphonic acid 9. 31P NMR (CDCl ) d: 6.5.
3
18O-[Methoxy(phenoxy)phosphoryl]methyl p-tolyl sulfoxide
(18O-10º). The crude phosphonic acid 9, prepared as above,
was dissolved in diethyl ether (5 mL) and an excess of diazo-
methane in diethyl ether (5 mL) was added. After 15 min, the
solvent was removed under vacuum a†ording the crude sulf-
oxide 18O-10@ as a mixture of two diastereoisomers in a 1.2 : 1
3
3
2
3.82 (3H, d, J \ 11.1 Hz, CH OP); 7.07È7.40 (9H, m,
3
aromatic). 31P NMR (CDCl ) d: 21.9; HRMS (EI): M`,
found 308.0634; C
3
H
O PS requires 308.0636.
15 17
3
[Methoxy(phenoxy)phosphoryl]methyl p-tolyl sulfoxide (10).
To a solution of sulÐde 11 (0.16 g, 0.5 mmol) in methanol (1
mL), catalyst (0.1 g) and hydrogen peroxide (2 mmol) were
added with stirring. The catalyst was prepared by mixing 96%
H SO (1.38 g) and 2-propanol (30 g). After completion of the
ratio [31P NMR (CDCl ) d: 15.0 and 14.6]. PuriÐcation by
3
thin layer chromatography gave 0.04 g (82% yield) of the pure
title sulfoxide.
2
4
oxidation (5 h), water (10 mL) was added to the reaction
mixture and the solution was extracted with chloroform
Acknowledgements
One of us (M. M.) thanks the Alexander von Humboldt Foun-
dation for conferment of the research prize that made realis-
ation of this work possible.
(3 ] 20 mL). The organic extracts were dried over MgSO
4
and evaporated to give, in almost quantitative yield (0.16 g,
98.8%), sulfoxide 10 (mixture of diastereoisomers) as an oil.
31P NMR (CDCl ) d: 15.0 and 14.7 (1 : 1.1); 1H NMR
3
(CDCl ) d: 2.42 (3H, s, CH Ph); 3.29È3.64 (2H, m, CH P);
3
3
2
3.78 and 3.89 (3H, 2 d, J \ 11.5 Hz, CH OP); 7.13È7.39 (7H,
m, aromatic); 7.63 (2H, aromatic). HRMS (EI): M`, found
3
References
324.0584; C
H
O PS requires 324.0585.
1
M. Miko¡ajczyk, W. H. Midura, B. Wladislaw, F. C. Biaggio,
M. W. Wieczorek and J. B¡aszczyk, T etrahedron, 1997, 53, 2959.
M. Miko¡ajczyk and A. Zatorski, Synthesis, 1973, 669.
M. Miko¡ajczyk, W. H. Midura, S. Grzejszczak, A. Zatorski and
A. Chefczynska, J. Org. Chem., 1978, 43, 473; M. Miko¡ajczyk,
W. H. Midura and M. Kajtar, Phosphorus Sulfur Relat. Elem.,
1988, 36, 79.
15 17
4
18O-(Diphenoxyphosphoryl)methyl p-tolyl sulfoxide (18O-8).
To a magnetically stirred solution of the sulÐde 12 (0.37 g,
1mmol) in methylene chloride (3 mL) was added at room tem-
perature a solution of 18O-labelled water (0.1 mL) in pyridine
(0.5 mL), followed by dropwise addition of a solution of
bromine (0.16 g) in methylene chloride (3 mL). Vigorous stir-
ring was continued for 8 h and then the excess bromine was
2
3
4
5
For a summary see: M. Miko¡ajczyk and P. Ba¡czewski, in
Advances in Sulfur Chemistry, ed. E. Block, JAI Press, Inc.,
Greenwich, CT, USA, 1994, vol. 1, pp. 41È96.
M. Miko¡ajczyk, S. Grzejszczak and A. Zatorski, J. Org. Chem.,
1975, 40, 1979; for a recent paper on this subject, see: van J. H.
Steenis, van J. J. G. S. Es and van der A. Gen, Eur. J. Org. Chem.,
2000, 2787.
destroyed by addition of anhydrous NaHSO (0.3 g). The
3
organic solvent was evaporated and the residue was shaken
with two portions of benzene (10 mL). The combined benzene
solution was dried over MgSO and evaporated to give a
6
7
G. Cevasco, S. Penco and S. Thea, Phosphorus, Sulfur Silicon
4
mixture of the sulfoxide 18O-8 and the corresponding sulfone
Relat. Elem., 1993, 84, 257.
in a 1 : 1 ratio. Column chromatography (petroleum etherÈ
acetone) gave pure sulfoxide 18O-8 as an oil (0.12 g, 31%
yield). 31P NMR (CDCl ) d: 9.6. 1H NMR (CDCl ) d: 2.41 (s,
F. Montanari, R. Danieli, H. Hogeveen and G. Maccagnani,
T etrahedron L ett., 1964, 2685; M. Cinquini, S. Colonna and F.
Montanari, T etrahedron L ett., 1966, 3181; M. Cinquini, S.
Colonna and F. Montanari, J. Chem. Soc. C, 1970, 572.
J. Drabowicz, W. H. Midura and M. Miko¡ajczyk, Synthesis,
1979, 39; A. Okruszek, J. L abelled Compd. Radiopharm., 1983, 20,
741.
3
3
3H, CH Ph): 3.56 and 3.65 (2H, AB part of an ABX system,
8
3
J
\ 14.7, J \ 14.8, J \ 15.1 Hz, CH P); 7.1È7.35 (m,
12H, aromatic); 7.66 (2H, aromatic).
HhH
HhP
HhP
2
New J. Chem., 2001, 25, 1073È1077
1077