SPECIMEN EXPERIMENTAL
General techniques: All reactions requiring anhydrous conditions were conducted in flame-dried
glass apparatus under an atmosphere of N2. THF and Et2O were freshly distilled from sodium
benzophenone ketyl prior to use. DMSO and DMF were distilled from CaH2 at 15 mmHg.
CH2Cl2 was freshly distilled from CaH2 and PhMe was distilled from molten sodium metal.
Anhydrous MeOH was obtained by distillation from its magnesium alkoxide and stored under N2
over activated 4Å molecular sieves. Preparative chromatographic separations were performed on
EM Science silica gel 60 (35-75 m) and reactions followed by TLC analysis using SigmaAldrich silica gel 60 plates (2-25 m) with fluorescent indicator (254 nm) and visualized with
UV, phosphomolybdic acid or p-anisaldehyde. All commercially available reagents were
purchased from Aldrich and were used as received unless otherwise noted.
Melting points were recorded using open capillary tubes on a Griffin melting point apparatus and
are uncorrected. Specific optical rotations were measured at ambient temperature (22 °C) from
CHCl3 solutions on an Optical Activity AA-1000 polarimeter using a 1 mL cell with 0.2 dm path
length. Infra-red spectra were recorded on a Perkin Elmer Spectrum One FT-IR spectrometer
using a thin film supported between NaCl plates or KBr discs where stated. 1H and 13C NMR
spectra were recorded in Fourier transform mode at the field strength specified on Bruker
Avance FT-NMR spectrometers. Spectra were obtained from the specified deuterated solvents in
5 mm diameter tubes. Chemical shift in ppm is quoted relative to residual solvent signals
calibrated as follows: CDCl3 H (CHCl3) = 7.26 ppm, C = 77.2 ppm; (CD3)2SO H
(CD3SOCHD2) = 2.50 ppm, C = 39.5 ppm; C6D6 H (C6HD5) = 7.16 ppm, C = 128.0 ppm;
CD3OD H (CHD2OD) = 3.31 ppm, C = 49.0 ppm; (CD3)2CO H (CD3COCHD2) = 2.05 ppm,
C = 29.8 ppm. Multiplicities in the 1H NMR spectra are described as: s = singlet, d = doublet, t
= triplet, q = quartet, m = multiplet, br = broad; coupling constants are reported in Hz. Numbers
in parentheses following carbon atom chemical shifts refer to the number of attached hydrogen
atoms as revealed by the DEPT spectral editing technique. Electron-impact (EI), chemical
ionisation (CI), and fast atom bombardment (FAB) mass spectra (MS and HRMS) were obtained
with a Micromass VG Autospec spectrometer. Electrospray (ES) mass spectra (MS and HRMS)
were obtained with a Micromass LCT spectrometer. Ion mass/charge (m/z) ratios are reported as
values in atomic mass units.
SPECIMEN EXPERIMENTAL
Laboratory notebook reference: PRB108.
(a) 1.2 eq LDA
THF, –78 °C
O
N
O
C12H12N2O2
(216.24)
N
(b)
Cl
Cl
Br
Br
Cl
(326) Cl
O
N
O
N
Br
C12H11BrN2O2
(295.13)
8-Bromo-7-(dimethylaminocarbonyloxy)quinoline: A solution of i-Pr2NH (2.06 mL, d =
0.722, 1.49 g, 14.8 mmol) in anhydrous THF (20 mL) at –20 °C under N2 was treated dropwise
with n-BuLi (9.64 mL, 1.47 M in hexanes, 14.2 mmol) and stirred for 5 min. The resulting
solution of LDA was further cooled to –78 °C and 7-(dimethylaminocarbonyloxy)quinoline
(2.55 g, 11.8 mmol) in anhydrous THF (15 mL) added carefully over 3 min down the cold flask
side-wall. The dark brown solution of lithiated quinoline was stirred for 40 min at –78 °C and
then added via cannula over 5 min to a similarly cooled solution of 1,2-dibromotetrachloroethane
(7.69 g, 23.6 mmol) in anhydrous THF (30 mL). The cooling bath was removed and the light
yellow reaction mixture allowed to stir for 45 min while slowly warming to rt. Sat. aq. NH 4Cl
(10 mL) was added and the mixture partitioned between EtOAc (20 mL) and H2O (10 mL). The
layers were separated and the aqueous phase was extracted with EtOAc (10 mL). The combined
organic extracts were washed with brine (10 mL), dried (Na2SO4) and concentrated in vacuo.
The crude residue (8.21 g) was further purified by column chromatography (eluting with 50-75%
EtOAc in hexanes) to yield the bromoquinoline (2.47 g, 8.4 mmol, 71%) as a light yellow solid.
A small sample of the material was recrystallised from THF to afford large colourless prisms:
mp 122-124 °C (THF); []D + 00.0 (c 1.00, CHCl3); IR (neat) 2951, 1709, 1597, 1355, 1048,
980, 949, 856, 826, 743, 667, 642, 568, 510 cm–1; 1H NMR (300 MHz, CDCl3)  9.05 (1H, dd, J
= 4.3, 1.7 Hz), 8.18 (1H, dd, J = 8.2, 1.7 Hz), 7.80 (1H, d, J = 8.8 Hz), 7.49 (1H, d, J = 8.8 Hz),
7.46 (1H, dd, J = 8.2, 4.3 Hz), 3.26 (3H, s), 3.08 (3H, s) ppm; 13C NMR (75 MHz, CDCl3) 
153.7 (0), 151.6 (1), 150.4 (0), 146.3 (0), 136.6 (1), 127.8 (1), 127.3 (0), 123.8 (1), 121.5 (1),
117.5 (0), 37.1 (3), 36.9 (3) ppm; MS (ES) m/z 297 (M+H)+, 295 (M+H)+; HRMS (ES) m/z
295.0078 (calcd. for C12H12Br(79)N2O2: 295.0082); Anal. calcd. for C12H11BrN2O2: C, 48.84; H,
3.76; N, 9.49. Found: C, 48.95; H, 3.75; N, 9.60.