F
Y. Cai et al.
Letter
Synlett
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(61) (E)-N,N-Diethyl-2-(4-toluenesulfonyl)ethylenamine
(3a);
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Typical Procedure
A 10 mL round-bottomed flask equipped with magnetic stirring
bar was charged with TsCl (1a; 0.2 mmol), Et3N (2a; 1 mmol),
eosin Y (3 mol%), K2HPO4 (1.5 equiv), and 1:2 EtOH–acetone (6
mL). The solution was then irradiated with 3 W blue LEDs at –5
to 5 °C under air. When the reaction was complete (TLC), the
solvent was removed under reduced pressure and the crude
product was purified by column chromatography [silica gel, PE–
EtOAc (5:1)] to give a brown oil; yield: 31.48 mg (67%). 1H NMR
(400 MHz, CDCl3): δ = 7.75 (d, J = 8.2 Hz, 2 H), 7.31 (d, J = 12.7
Hz, 1 H), 7.27 (d, J = 8.0 Hz, 2 H), 4.91 (d, J = 12.7 Hz, 1 H), 3.18
(br d, 4 H), 2.41 (s, 3 H), 1.17 (s, 6 H). 13C NMR (100 MHz, CDCl3):
δ = 148.5, 142.3, 141.8, 128.5, 125.9, 91.4, 49.8, 42.4, 21.2, 14.5
11.0. HRMS (ESI): m/z [M + Na]+ calcd for C13H19NNaO2S+:
276.1020; found: 276.1029.
(62) N,N-Diethyl-4-toluenesulfonamide (4a); Typical Procedure
A 10 mL round-bottomed flask equipped with magnetic stirring
bar was charged with TsCl (1a; 0.2 mmol), Et3N (2a; 1 mmol),
eosin Y (3 mol%), K2HPO4 (1.5 equiv), and 1:1 MeCN–H2O (6
mL). The solution was then irradiated with 12 W blue LEDs at r.t.
under an O2 atmosphere. When the reaction was complete
(TLC), the solvent was removed under reduced pressure and the
crude product was purified by column chromatography [silica
gel, PE–EtOAc (5:1)] to give a white solid; yield: 34.06 mg (75%);
mp 60–62 °C. 1H NMR (400 MHz, CDCl3): δ = 7.70 (d, J = 8.1 Hz, 2
H), 7.30 (d, J = 8.0 Hz, 2 H), 3.23 (q, J = 7.2 Hz, 4 H), 2.43 (s, 3 H),
1.13 (t, J = 7.1 Hz, 6 H). 13C NMR (100 MHz, CDCl3): δ = 142.8,
137.2, 129.4, 126.9, 41.9, 21.3, 14.0. HRMS (ESI): m/z [M + Na]+
calcd for C11H17NNaO2S+: 250.0872; found: 250.0898.
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© Georg Thieme Verlag Stuttgart · New York — Synlett 2017, 28, A–F