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M. Barbero et al.
LETTER
I.; Fochi, R.; Regondi, V. Gazz. Chim. Ital. 1986, 116, 165.
(g) Sørbye, K.; Tautermann, C.; Carlsen, P.; Fiksdahl, A.
Tetrahedron: Asymmetry 1998, 9, 681. (h) Karino, H.;
Goda, H.; Sakamoto, J.-I.; Yoshida, K.; Nishiguchi, H.
WO96/33167, 1996; Chem. Abstr. 1997, 126, 18657.
drying under vacuum, pure salts 3 were obtained and
immediately reacted (physical and 1H NMR and 13C NMR
spectral data identical to literature).
Conversion of Crude Salts 3 to O-Ethyl S-Aryl
Dithiocarbonates 4 and Oxidative Chlorination of
Crudes 4 to Arenesulfonyl Chlorides 5 – General
Procedures
(3) (a) Garcia-Garcia, P.; Lay, F.; Garcia-Garcia, P.; Rabalakos,
C.; List, B. Angew. Chem. Int. Ed. 2009, 48, 4363.
(b) Treskow, M.; Neudörfl, J.; Giernoth, R. Eur. J. Org.
Chem. 2009, 3693.
(4) (a) Hoyle, J. In The Chemistry of Sulphonic Acids, Esters
and their Derivatives; Patai, S.; Rappoport, Z., Eds.; Wiley:
New York, 1991, 379–386. (b) Nishiguchi, A.; Maeda, K.;
Miki, S. Synthesis 2006, 4131.
(5) (a) Barbero, M.; Cadamuro, S.; Degani, I.; Fochi, R.;
Regondi, V. EP 234249, 1987; Chem. Abstr. 1988, 108,
23697. (b) Barbero, M.; Cadamuro, S.; Degani, I.; Fochi, R.;
Regondi, V. Synthesis 1989, 957. (c) Barbero, M.;
Cadamuro, S.; Degani, I.; Fochi, R. IT 0001245596, 1991.
(6) Romagnoli, R.; Baraldi, P. G.; Carrion, M. D.; Cara, C. L.;
Preti, D.; Fruttarolo, F.; Pavani, M. G.; Tabrizi, M. A.;
Tolomeo, M.; Grimaudo, S.; Di Cristina, A.; Balzarini, J.;
Hadfield, J. A.; Brancale, A.; Hamel, E. J. Med. Chem. 2007,
50, 2273.
(7) Damschroder, R. E.; Peterson, W. D. Org. Synth., Coll. Vol.
III 1955, 106.
(8) (a) Leuckart, R. J. Prakt. Chem. 1890, 41, 179. For
reviews, see: (b) Baguley, P. A.; Walton, J. C. Angew.
Chem. Int. Ed. 1998, 37, 3072. (c) Studer, A. Synthesis
2003, 835.
(9) (a) Barbero, M.; Degani, I.; Fochi, R.; Perracino, P. WO 98/
39312, 1998; Chem. Abstr. 1998, 129, 244942. (b) Barbero,
M.; Crisma, M.; Degani, I.; Fochi, R.; Perracino, P.
Synthesis 1998, 1171.
(10) (a) Wang, C.; Hamilton, C.; Meister, P.; Menning, C. Org.
Process Res. Dev. 2007, 11, 52. (b) Percec, V.; Bera, T. K.;
De B, B.; Sanai, Y.; Smith, J.; Holerca, M. N.; Barboiu, B.
J. Org. Chem. 2001, 66, 2104.
Crude salts 3 (1.0 mmol) were carefully added under stirring
to a solution of potassium O-ethyl dithiocarbonate (1.0
mmol, 1.60 g) and Na2CO3 (1.0 mmol, 1.06 g) in H2O (40
mL), heated to 35–40 °C. Then the reaction mixture was
stirred at 60 °C for 20 min. After cooling to r.t., the resultant
mixture was poured into Et2O–H2O (40 mL, 2:1). The
aqueous layer was separated and extracted with Et2O (2 × 20
mL). The combined organic extracts were washed with H2O
(20 mL), dried over Na2SO4, and evaporated. The crude
residues were directly reacted to give arenesulfonyl
chlorides 5. A small stream of Cl2 was bubbled through a
well-stirred ice-cooled emulsion of crudes 4 in H2O (20 mL)
or HCOOH–H2O (40 mL, 9:1; for crude 4f), at such a rate
that the temperature did not rise to 10 °C. The reaction was
stopped when Cl2 was no longer absorbed and TLC analysis
(PE–Et2O, 8:2) showed the presence of only one persistent
spot. After removing chlorine excess, the reaction mixture
was extracted with CH2Cl2 (3 × 20 mL); organic extracts
were neutralized with 10% aq NaHCO3, dried, and
evaporated under reduced pressure. Crude residues
chromatographed on a short column (PE–Et2O, 9:1)
provided pure arenesulfonylchlorides 5 (comparison with
literature data or commercially pure samples).
Benzene-1,2-disulfonyl Chloride (5f)2g
After completion of oxidative chlorination (TLC analysis
and appearance of a fine dispersed white solid), chlorine
excess was removed under vacuum; crude virtually pure 5f
was filtered on a Büchner funnel and washed with cold H2O.
Mp 143–144 °C (CCl4; lit. 143–144 °C).2f 1H NMR (200
MHz, CDCl3): d = 8.04–8.11 (m, 2 H), 8.45–8.53 (m, 2 H).
13C NMR (50 MHz, CDCl3): d = 132.6 (2 C), 136.4 (2 C),
141.4 (2 C). MS (EI): m/z (%) = 274 (20) [M+].
(11) Barbero, M.; Degani, I.; Dughera, S.; Fochi, R.; Perracino, P.
Synthesis 1999, 90.
(12) Farrar, W. V. J. Chem. Soc. 1960, 3063.
(13) Limpricht, H. Liebigs Ann. Chem. 1891, 261, 310.
(14) Barber, H. J.; Smiles, S. J. Chem. Soc. 1928, 1141.
(15) (a) Armarego, W. L. F.; Turner, E. E. J. Chem. Soc. 1956,
1665. (b) Armarego, W. L. F.; Turner, E. E. J. Chem. Soc.
1957, 13.
(16) Aikawa, K.; Mikami, K. Chem. Commun. 2005, 5799.
(17) Robinson, M. K.; Kochurina, V. S.; Hanna, J. M.
Tetrahedron Lett. 2007, 48, 7687.
Biphenyl-2,2¢-disulfonyl Chloride (7)
Mp 143–144 °C (CHCl3–PE; lit. 144–145 °C).23 Prepared by
suspending crude 17 in CH2Cl2/H2O (10 mL, 10:1) and
reacting with excess chlorine at 0–10 °C for 30 min; then
HCOOH (10 mL) was added, and chlorination was
continued until only two persisting spots were present on
TLC analysis. By column chromatography (CH2Cl2–MeOH,
99:1), disulfonyl chloride 7 was eluted as first product (Rf =
0.8); the second eluted product was 13 (Rf = 0.3); mp 143–
144 °C (CHCl3–PE; lit.23 144–145 °C). 1H NMR (200 MHz,
CDCl3): d = 7.49 (dd,, J = 1.8, 7.2 Hz, 1 H), 7.67 (td, J = 1.8,
7.6 Hz, 1 H), 7.75 (td, J = 1.6, 7.6 Hz, 1 H), 8.20 (dd, J = 1.6,
8.0 Hz, 1 H). 13C NMR (50 MHz, CDCl3): d = 129.0 (2 C),
129.8 (2 C),132.0 (2 C), 134.3 (2 C), 135.7 (2 C), 142.6
(2 C).
(18) Darses, S.; Jeffery, T.; Genet, J.-P. Tetrahedron Lett. 1996,
37, 3857.
(19) Barbero, M.; Degani, I.; Dughera, S.; Fochi, R. J. Org.
Chem. 1999, 64, 3448.
(20) Bhar, D.; Chandrasekaran, S. Synthesis 1994, 785.
(21) Fabbri, D.; Delogu, G.; De Lucchi, O. J. Org. Chem. 1993,
58, 1748.
(R)-Binaphthyl-2,2¢-disulfonyl Chloride (8)
(22) Diazotization of Amines 2 – General Procedure
To a stirred solution of amines 2 (1.0 mmol) and HBF4 (54%
in Et2O. 1.2 mmol. 1.90 g) in HCOOH (15 mL), at 5–10 °C,
3-methylbutyl nitrite (1.29 g, 1.1 mmol) was slowly added at
such a rate that the temperature did not exceed 10 °C. Then
the reaction mixture was stirred for 10 min in an ice bath, and
at r.t. for 5 min. Finally, after cooling at 0–5 °C, anhyd Et2O
was added to precipitate salts 3, gathered by filtration on a
Büchner funnel, and washed several times with Et2O. After
Colorless needles; mp 241.2–242.2 °C (CHCl3–PE; lit.
244.3 °C).3b 1H NMR (200 MHz, CDCl3): d = 7.09 (d,
J = 8.6 Hz, 2 H), 7.38 (ddd, J = 1.4, 7.0, 8.6 Hz, 2 H), 7.65
(ddd, J = 1.2, 7.0, 8.2 Hz, 2 H), 8.00 (d, J = 8.4 Hz), 8.20 (d,
J = 9.0 Hz, 2 H), 8.27 (d, J = 9.0 Hz, 2 H). 13C NMR (50
MHz, CDCl3): d = 123.2 (2 C), 127.9 (2 C), 128.4 (2 C),
128.5 (2 C), 130.1 (2 C), 131.0 (2 C), 131.8 (2 C), 133.6
(2 C), 135.3 (2 C), 140.7 (2 C).
(23) Chau, M. M.; Kice, J. L. J. Org. Chem. 1977, 42, 3265.
Synlett 2010, No. 12, 1803–1806 © Thieme Stuttgart · New York