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10
Procedure for
the Synthesis of Xanthate 1a: To a solution of tetramethylmethylenebis-phosphonate
(1.16 g, 5 mmol) in anhyd THF (50 mL) at r.t. under argon was added portionwise
60% NaH in mineral oil (0.4 g, 10 mmol). When the evolution
of hydrogen ceased, the reaction mixture was cooled down to -78 °C
and a solution of bis-ethoxythio-carbonyldisulfane (1.27 g, 5.25
mmol) in anhyd THF (10 mL) was added. The reaction mixture was then
slowly warmed to r.t. A 1 M HCl solution was added (50 mL) and the
mixture was extracted with diethyl ether (2 × 50
mL). The combined organic extracts were washed with sat. aq NaCl,
dried over MgSO4, filtered, and the solvents were removed
under reduced pressure. The residue was purified by flash column
chromatography (silica gel, dichloro-methane/methanol,
97:3) to give 1a (1.28 g, 73%)
as a pale yellow oil. 1H NMR (400 MHz, CDCl3): δ = 1.45
(t, J = 7.0 Hz,
3 H), 3.84-3.87 (m, 12 H), 4.70 (q, J = 7.0
Hz, 2 H), 4.91 (t, J = 21.7
Hz, 1 H). 13C NMR (50 MHz, CDCl3): δ = 13.8, 41.5
(t, J
CP
= 137 Hz), 54.4 (d, J
CP
= 9 Hz), 72.3, 211.9.
IR (CCl4): 2955, 1459, 1264, 1239, 1184, 1112, 1042 cm-1.
MS (CI + NH3): m/z = 353
(MH+), 370 (MNH4
+).
11
Typical Procedure: 352
mg (1 mmol) of xanthate 1a and 0.33 mL
(2 mmol) of allyl acetate dissolved in 1,2-dichloroethane (1 mL)
were refluxed a few minutes under argon before the addition of (20
mg, 0.05 mmol) of commercially available lauroyl peroxide. The reflux
was maintained for another 2 h. The solvent was then removed under
reduced pressure and the residue purified by flash column chromatography
(silica gel, dichloromethane/methanol, 97:3) to give 2b (370 mg, 82%) as a pale yellow oil. 1H
NMR (400 MHz, CDCl3): δ = 1.41 (t, J = 7.0 Hz,
3 H), 2.05 (s, 3 H), 2.02-2.22 (m, 1 H), 2.28-2.41
(m, 1 H), 2.66 (tdd, J = 25.0,
8.8, 3.5 Hz, 1 H), 3.78-3.82 (m, 12 H), 4.19 (dd, J = 11.1,
5.3 Hz, 1 H), 4.24-4.30 (m, 1 H), 4.34 (dd, J = 11.1,
4.1 Hz, 1 H), 4.62 (q, J = 7.0
Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 13.8,
20.8, 26.3 (t, J
CP
= 4 Hz), 33.4 (t, J
CP
= 134 Hz), 48.5, 53.5
(d, J
CP
= 9 Hz), 65.6, 70.5,
170.6, 212.0. IR (CCl4): 2954, 1748, 1257, 1227, 1036 cm-1.
MS (CI + NH3): m/z = 453
(MH+). Anal. Calcd for C13H26O9P2S2:
C, 34.51; H, 5.79. Found: C, 34.61; H, 5.88.
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