Toluenesulfonylbromide, steppingstone to M/Ethyltosylate, relatively gentle alkylating agents. Ethyltosylate can also be used to make nitroethane[1] but there's other fun things you can do with tosylbromide,too. See some related buzz at
Post 417550
(Antoncho: "Methyl tosylate: _finally_ , OTC!!!", Novel Discourse). What I want to discuss here is an alternate synthesis pathway: MePhSO3Na + Ph3P*Br2. That can be found in [2], which should be easily retrievable using a test account as described in
Post 363228
(Rhodium: "Free Online Chemistry & Medicinal Journals", Novel Discourse), I wasn't able to establish a connection to the Thieme server for the last ~20h so I'd be most grateful if someone could post here what the article says.
Concerning the Ph3P*Br2 [3]:
To an ice-water bath cooled solution of PPh3 (457mg, 1.74mmol) in 4ml of CH2Cl2
under argon was added Br2 (0.87 mL, 1.7mmol). after an additional 5min ... they
add a diol here ... what's important is that after 5min the PPh3 + Br2 --> Ph3P*Br2
rxn is complete enough to proceed. Well, I pretty much hate them for doing it so
microscale, but you see that it is mainly cool, add, stir, wait. Why do they use Ar ?
[1]Rodionow; BSCFAS; Bull.Soc.Chim.Fr.; <4> 39; 1926; 318; BSCFAS; Bull.Soc.Chim.Fr.; <4> 45; 1929; 119.
[2]Kataoka, Tadashi; Iwama, Tetsuo; Setta, Tomofumi; Takagi, Atsuko; SYNTBF; Synthesis; EN; 4; 1998; 423-426
[3]McPhee, Mark M.; Kerwin, Sean M.; BMECEP; Bioorg.Med.Chem.; EN; 9; 11; 2001; 2809 - 2818
see also:
Roy, Aroop K.; JACSAT; J.Amer.Chem.Soc.; EN; 115; 7; 1993; 2598-2603 and
Freydank, Anke C.; Humphrey, Mark G.; Friedrich, Reiner W.; Luther-Davies, Barry; TETRAB; Tetrahedron; EN; 58; 7; 2002; 1425 - 1432
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