Aliquots of these solutions (1.5 cm3) were then added to
weighed amounts of quaternary ammonium salts in nmr tubes
and thoroughly mixed (t = 0). 1H nmr spectra were then
recorded at intervals.
3 A. Mäntylä, J. Vepsäläinen, T. Järvinen and T. Nevalainen,
Tetrahedron Lett., 2002, 43, 3793.
4 (a) M. Mueller, Chem. Ber., 1873, 6, 227; T. Purgold, Chem. Ber.,
1873, 6, 502; (b) R. V. Jones, U. S. Patent 2,860,123, 1958 (Chem.
Abs., 1959, 53, 4797).
For reactions in the CDCl3/H2O two phase system, stock
solutions of CMCS, MBCS or MCS together with the same
internal standards in CDCl3 were prepared with concentrations
as specified above. Weighed amounts of the salt of the nucleo-
phile together with tetraoctylammonium bromide (5 mol% with
respect to the organic chlorosulfate) were placed in a small
flask together with water (5 cm3) and equilibrated at 25 ЊC. An
aliquot of the CDCl3 solution (5 cm3) was added with vigorous
magnetic stirring (t = 0) and the spectrum of the organic layer
recorded at appropriate intervals.
5 (a) K. Fuchs and E. Katscher, Chem. Ber., 1927, 60, 2288; K. Fuchs
and E. Katscher, British Patent 299,064, 1928 (Chem. Abs., 1929, 23,
2990); (b) Reactions of chlorosulfuric acid with a variety of aliphatic
compounds including haloalkanes have been reviewed by R. J.
Cremlyn, Chlorosulfonic acid, a versatile reagent, Royal Society of
Chemistry, Cambridge, 2002, p. 153.
6 M. Y. Kraft and B. A. Alekseev, Zh. Obsh. Khim., 1932, 2,
726.
7 E. J. Geering and Occidental Chemical Corporation, U. S. Patent
4649209, 1987.
8 (a) H. K. Hall Jr., J. Am. Chem. Soc., 1956, 78, 1450; (b) R. L.
Burwell, J. Am. Chem. Soc., 1952, 74, 1462; (c) J. Zawidski and
J. Saykowski, Anzeig. Akad. Wis. Krakau, 1916, 73 (Chem. Abs.,
1917, 11, 2294).
Reaction of CMCS with sodium phenoxide
Phenol (5.08 g) was added to tetrahydrofuran (20 cm3) contain-
ing sodium hydride (7.3 g of a 60% dispersion in oil, prewashed
with cyclohexane) under a positive pressure of argon. After
hydrogen evolution had ceased, a solution of CMCS (17.86 g)
in tetrahydrofuran (20 cm3) was added dropwise at room tem-
perature over a period of one hour and the mixture allowed to
stir overnight. The reaction mixture was then diluted with ethyl
acetate and the insoluble salts removed by centrifugation and
then filtration. Removal of the solvent left a gelatinous material
that was redissolved in ethyl acetate, the solution washed with
water and dried (MgSO4). Rotary evaporation left a red oil
(8.96 g), TLC of which showed two spots, one corresponding to
phenol and the other to the product, the Rf-value of which was
close to that of CMCS. Vacuum distillation of the oil afforded
phenoxymethyl chlorosulfate (4.37 g; 37% yield) bp128 ЊC/9
mm Hg as a colourless oil. Analysis: found, C 37.9, H 3.2, S
14.2, Cl 16.4%; C7H7O4SCl requires C 37.8, H 3.2, S 14.4,
Cl 15.9%. Mass spectrum: accurate mass: found, 221.97544;
calculated, 221.97536; fragmentation 222 (Mϩ), 187 (– Cl), 107
(– SO3), 93 (– CH2), [77 (– CH2O)]. Nmr spectra (300 MHz/
CDCl3): δH 5.81 (s; 2H), 7.21–7.43(m; 5H): δC 76.55, 121.32,
128.02, 130.20, 150.26 ppm.
9 (a) E. Buncel and J. P. Millington, Can. J. Chem., 1965, 43, 556; for a
review of the chemistry of alkyl chlorosulfates, see : E. Buncel,
Chem. Rev., 1970, 70, 323.
10 G. Flint, Encyclopedia of Chemical Technology, Interscience, New
York, 1954, vol. 13, p. 501.
11 M. Schmidt and W. Siebert in Comprehensive Inorganic Chemistry,
ed. J. C. Bailar, H. J. Emeléus, R. Nyholm and A. F. Trotman-
Dickenson, Pergamon Press, Oxford, 1973, vol. 2, p. 864.
12 For recent discussions on SO3-cleavage vs. transfer between
molecules, see : G. Lowe, Philos. Trans. R. Soc. London, Ser. B, 1991,
332, 141; A. Williams, Acc. Chem. Res., 1989, 22, 387; A. Hopkins,
R. A. Day and A. Williams, J. Am. Chem. Soc., 1983, 105, 6062;
N. Bourne, A. Hopkins and A. Williams, J. Am. Chem. Soc., 1985,
107, 4327; D. Bethell, R. E. Fessey, E. Namwindwa and D. W.
Roberts, J. Chem. Soc., Perkin Trans. 2, 2001, 1489.
13 B. S. Yiin and D. W. Margerum, Inorg. Chem., 1988, 27,
1670.
14 See, for example: C. L. Liotta, E. E. Grisdale and H. P. Hopkins,
Tetrahedron Lett., 1975, 4205; S. Winstein, L. G. Savedoff, S. Smith,
I. D. R. Stevens and J. S. Gall, Tetrahedron Lett., 1960,9,24; A. J.
Parker, Adv. Phys. Org. Chem., 1967, 5, 173; A. J. Parker, Chem. Rev.,
1969, 69, 15.
15 E. E. Gilbert, Chem. Rev., 1962, 62, 549.
16 R. J. Gillespie and E. A. Robinson, Can. J. Chem., 1961, 39,
2189.
17 (a) See, for example: G. A. Olah and P. E. Peterson, J. Am. Chem.
Soc., 1968, 90, 4675; P. E. Peterson and J. F. Coffey, J. Am. Chem.
Soc., 1971, 93, 5208; P. E. Peterson, Acc. Chem. Res., 1971, 4,
407; G. A. Olah, Halonium ions, Wiley-Interscience, New York,
1973; (b) N. J. Head, G. Rasul, A. Mitra, A. Bashirheshemi,
G. K. S. Prakash and G. A. Olah, J. Am. Chem. Soc., 1995, 117,
12107.
18 J. K. Bosscher and H. Cerfontain, Rec. Trav. Chim. Pays-Bas, 1968,
87, 873; J. K. Bosscher and H. Cerfontain, Tetrahedron, 1968, 24,
6543; see also: D. W. Roberts, Org. Process Res. Dev., 2003, 7, 172;
J. O. Morley, D. W. Roberts and S. P. Watson, J. Chem. Soc., Perkin
Trans. 2, 2002, 538; for a general account of aromatic sulfonation
and earlier references, see: H. Cerfontain, Mechanistic Aspects in
Aromatic Sulfonation and Desulfonation, Interscience, New York,
1967, pp. 13–20.
Cyclic voltammetry
Cyclic voltammograms were recorded on solutions of CMCS
(1.06 mM), MBCS (3.0 mM) or MCS (5.9 mM) in CH3CN
containing tetrabutylammonium perchlorate (0.1 M) at room
temperature using a platinum working electrode (1 mm diam-
eter), a coil of platinum wire as counter electrode and a satur-
ated calomel electrode as reference. The electrode system was
controlled by an EcoChemie PGSTAT20 combined waveform
generator/potentiostat.
19 W. W. Binkley and E. F. Degering, J. Am. Chem. Soc., 1939, 61,
3250; W. Traube, Z. Angew. Chem., 1925, 38, 441; R. Levaillant,
C. R. Acad. Sci. Paris, 1933, 197, 648.
20 J. Charalambous, M. J. Frazer and W. Gerrard, J. Chem. Soc., 1964,
5480.
References
1 E. Binderup and E. T. Hansen, Synth. Commun., 1984, 14(9), 857.
2 N. Harada, M. Hongu, T. Tanaka, T. Kawaguchi, T. Hashiyama and
K. Tsujihara, Synth. Commun., 1994, 24, 767.
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 1 5 5 4 – 1 5 6 2
1562