5
8
B. Bittner et al. / Journal of Fluorine Chemistry 169 (2015) 50–60
Table 4 (Continued )
a
1
13
Prod.
Structure
H NMR (
d
, ppm)
C NMR (
d
, ppm)
9
6A
6B
10
9
1
4
IVb
7-Methyl-3,4,4a,5,8,8a-hexahydro-
1.42 (3H ), 1.55 (1H ), 1.65 (1H and 1H ),
23.7 q, (C ),
J
C,H = 125.3 Hz, 24.0 t, (C ),
3
A
3B
2A
5
1
3
1
2H-naphtha-len-1-one
1.68 (1H ), 1.79 (1H ), 2.08 (1H ), 2.17 (1H ),
JC,H = 125.8 Hz, 24.1 t, (C ), JC,H = 125.8 Hz,
2
B
4
11
7
6
1
10
2
.22 (1H ), 2.28 (2H ), 2.47 (1H ), 5.12 (1H )
28.4 t, (C ), JC,H =124.8 Hz, 32.1 t, (C ),
1
5
1
J
C,H = 124.8 Hz, 36.3 d, (C ), JC,H = 130.5 Hz,
2
1
11
3
9.9 t, (C ), JC,H =126.7 Hz, 47.9 d, (C ),
1
7
1
J
C,H = 127.6 Hz, 118.1 d, (C ), JC,H = 154.4 Hz,
8
1
1
31.7 m, (C ), 212.6 m (C )
6
A
10
8
5
10
1
8
V
6,7-Dimethyl-3,4,4a,5,8,8a-hexahydro-
1.39 (1H ), 1.56 (3H ), 1.59 (3H ), 1.65 (1H ),
18.8 q, (C ), JC,H = 124.9 Hz, 19.1 q, (C ),
4
A
6B
11A
3A
1
4
1
2H-naphthalen-1-one
1.66 (1H ), 1.88 (1H and 1H ), 2.00 (1H ),
JC,H = 124.9 Hz, 26.4 t, (C ), JC,H = 128.5 Hz,
1
1B
4B
3B
12
3
1
6
2
2
.03 (1H
and 1H ), 2.15 (1H ), 2.18 (1H ),
31.1 t, (C ), JC,H =126.4 Hz, 32.6 t, (C ),
2
A
2B
1
11
1
.31 (1H ), 2.37 (1H
)
JC,H = 125.5 Hz Hz, 40.4 t, (C ), JC,H = 126.3 Hz,
5
1
2
4
1.1 d, (C ), JC,H = 125.3Hz, 42.1 t, (C ),
1
12
1
J
C,H = 128.0 Hz, 51.3 d, (C ), JC,H = 123.0 Hz,
9
7
1
1
24.2 m, (C ), 124.8 m (C ) 212.7 m, (C ).
2
,7
3A
7A
7B
4A
4
1
3
VIa
endo-Tricyclo[6.2.1.0 ]undec-9-en-3-one
0.66 (1H ), 1.20 (H ), 1.33 (1H ), 1.64 (1H ),
21.9 t, (C ), JC,H =127.5 Hz, 28.0 t, (C ),
4
B
3B
2A
2B
1
2
1
1
2
5
.82 (1H ), 1.84 (1H and 1H ), 2.20 (1H ),
JC,H = 127.7 Hz, 39.4 t, (C ), JC,H = 125.4 Hz,
5
11
6
10
5
1
10
.56 (1H ), 2.60 (1H ), 2.77 (1H ), 3.14 (1H ),
41.4 d, (C ), JC,H = 137.9 Hz, 45.2 d, (C ),
9
8
1
6
1
.90 (1H ), 6.06 (1H )
JC,H = 151.7 Hz, 46.6 d, (C ), JC,H = 145.4 Hz,
7
1
11
4
8.3 t, (C ), JC,H =133.4 Hz, 51.7 d, (C ),
1
9
1
J
C,H = 128.6 Hz, 134.9 d, (C ), JC,H = 169.4 Hz,
8
1
1
1
37.7 d, (C ), JC,H = 171.2 Hz, 215.2 m, (C )
2
,7
10A
4A
4B
9
1
10
VIb
exo-Tricyclo[6.2.1.0 ]undec-9-en-3-one
0.82 (1H ), 1.06 (1H ), 1.17 (1H ), 1.50
21.8 t, (C )
J
C,H = 129.3 Hz, 29.7 t, (C
)
9
A
9B
2
10
1
11 1
(
1H ), 1.87 (1H ), 1.95 (1H and 1H ), 2.10
J
C,H = 127.9 Hz, 39.2 t, (C
)
J
C,H = 125.7 Hz,
1
1A
11B
8
3
7 1
4
(
1H ), 2.32 (1H ), 2.50 (1H ), 2.77 (1H ),
44.2 d, (C ) JC,H = 150.7 Hz, 44.5 t, (C )
7
6
5
1
3 1
3
.19 (H ), 5.55 (1H ), 5.97 (1H )
JC,H = 133.6 Hz, 45.2 d, (C ) JC,H = 150.2 Hz,
8
1
2
4
7.0 d, (C ) JC,H = 147.6 Hz, 50.2 d, (C )
1
5 1
J
C,H = 135.0 Hz, 135.5 d, (C ) JC,H = 169.4 Hz,
6
1
1
1
37.8 d, (C ) JC,H = 170.9 Hz, 215.2 m, (C )
a
The numbering only serves as indicator for NMR characterization purposes.
1
transformation. The H NMR chemical shifts were referenced
as small as possible to get the best resolution possible. The
resolutions were in the range of 2 to 10 Hz. These resolutions
were lower than the resolutions of the corresponding 1D NMR
spectra recorded, so that the HMQC spectra were only used to
identify the relative positions of the resonances for assignment
purposes. The chemical shifts presented were taken from the 1D
NMR spectra.
with respect to tetramethylsilane (TMS) yielding the following
chemical shifts for the used solvents CDCl
.23 ppm) and CD CN (contains CD HCN: 1.96 ppm). The
NMR spectra were referenced with respect to tetramethylsilane
3 3
(contains CHCl :
1
3
7
3
2
C
(
TMS) using the chemical shifts for the solvents CDCl
3
(77.2 ppm)
F NMR chemical shifts were
using the internal standards C
1
9
3
and CD CN (118.7 ppm). The
referenced with respect to CFCl
ꢀ162.9 ppm) or C CF (ꢀ63.9 ppm). The P NMR chemical
shifts were referenced with respect to H PO (85%) in D O. A
3
6 6
F
3
1
(
6
H
5
3
3.3.2. Differential scanning calorimetry (DSC)
3
4
2
Thermal analyses were performed using a Mettler-Toledo DSC
1 system. The temperature range was 25 8C to 400 8C if not
otherwise stated. Samples were typically in the magnitude of 1–
11 mg. A temperature program was used to heat the furnace
(usually 10 K/min). Processing of the raw data was performed
positive (negative) sign denotes a chemical shift to high (low)
frequency of the reference compound.
2
D-HMQC NMR spectra: The 2D-HMQC NMR experiments (2D
H-1/X correlation via heteronuclear zero and double quantum
coherence with decoupling during acquisition and using gradient
pulses for selection) were all performed with standard pulse
sequences supplied by the spectrometer manufacturer. The HMQC
spectra were used to establish one-bond proton-carbon connectivi-
e
using the Star software [38].
3.3.3. Quantum-chemical calculations
Density Functional Theory (DFT) [39–41] calculations were
carried out using the long-range corrected (LC) and empirical
ties. The spectra were measured with 4096 f
2
data points, 2048
increments and 8 scans. The spectral windows were set individually
dispersion (D) corrected hybrid density functional
vB97X-D from