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16
General Experimental
Procedure for Direct Conversion of Olefins into α-Bromo
Ketones
To a stirred suspension of IBX (5.5 mmol)
and TEAB (5.5 mmol) in anhydrous CH2Cl2 was
added the olefine (5 mmol). Within 5-15 min the reaction
mixture turned from yellow to colorless and homogeneous, indicating
completion of reaction (monitored by TLC). The reaction mixture
was diluted with CH2Cl2 (25 mL) and washed
with sat. NaHCO3 (2 × 25 mL),
followed by NaHSO3 (25 mL), and brine (25 mL). The organic
layer was separated, dried over anhyd Na2SO4,
filtered, and solvent was evaporated under reduced pressure to give
the crude bromo ketone. The crude product was purified by column
chromatography using silica gel (60-120), eluting with
EtOAc-PE (1:99).
17
Spectroscopic
Data for Selected α-Bromo Ketones
2-Bromocyclohexanone (Entry 2)
Liquid.¹³a IR
(neat): νmax = 1731,
740, 680 cm-¹. ¹H
NMR (60 MHz, CDCl3): δ = 1.25-2.51
(m, 8 H), 3.82-4.13 (dd, J = 1.92
Hz, 1 H).
2-Bromocyclooctanone (Entry
3)
Liquid.¹³b IR (neat): νmax = 1730,
685 cm-¹. ¹H NMR
(60 MHz, CDCl3): δ = 1.25-1.59
(m, 8 H), 2.17-2.52 (m, 4 H), 4.08-4.17 (t, J = 2.9 Hz,
1 H).
1-Bromoocta-2-one (Entry 4)
Liquid.¹4a IR
(neat): νmax = 1730,
686 cm-¹. ¹H NMR
(300 MHz, CDCl3): δ = 0.91-1.10
(t, J = 9.6
Hz, 3 H), 2.26-2.00 (m, 10 H), 3.74 (s, 2 H).
1-Bromo-3,3-dimethylbutan-2-one (Entry 6)
Liquid.¹4b IR
(neat): νmax = 1730,
690 cm-¹. ¹H NMR
(300 MHz, CDCl3) δ = 1.14
(s, 9 H), 3.69 (s, 2 H).
1-Bromo-3-phenoxypropan-2-one
(Entry 8)
Liquid.¹5a IR (neat): νmax = 1737,
668 cm-¹. ¹H NMR
(60 MHz, CDCl3): δ = 4.46
(s, 2 H), 5.10 (s, 2 H), 6.99-7.34 (m, 5 H).
1-Bromo-3-(4-chlorophenoxy)propan-2-one (Entry
9)
Liquid.¹5b IR (neat): νmax = 1738,
668 cm-¹. ¹H NMR
(300 MHz, CDCl3): δ = 4.46
(s, 2 H), 5.10 (s, 2 H), 7.03 (dd, J = 8.1
Hz, 2 H), 7.38 (dd, J = 6.4
Hz, 2 H).
10-Bromo-11-oxo-10,11-dihydro-5
H
-dibenzo[
b
,
f
]azepine-5-carboxamide
(Entry 10)
Solid; mp 89 ˚C.¹5c IR
(KBr): νmax = 3377,
3325, 3020, 1726, 1696, 744 cm-¹. ¹H
NMR (60 MHz, CDCl3): δ = 6.59 (s,
1 H), 6.99-7.92 (m, 8 H).
