Molecules 2019, 24, 3844
9 of 18
1
27.28 (CH); 127.14 (CH); 127.12 (CH); 126.67 (CH); 125.49 (C); 122.88 (C); 61.88 (CH ); 56.89 (CH )
2 2
+
ppm. HRMS (ESI) calculated for C H N [M − Br] : 1030.4407, found 1030.4412.
80
56
(
11bS,11b’S)-2,6-Bis(4-tritylphenyl)-3,3’,5,5’-tetrahydro-4,4’-spirobi[dinaphtho[2,1-c:1’,2’-e]azepin]-4-ium
bromide (1e): 7% yield. 1H-NMR
: 8.23 (s, 2H); 8.00 (d, J = 8.2 Hz, 2H); 7.69 (d, J = 8.2 Hz, 2H);
.49–7.55 (m, 4H); 7.41 (d, J = 8.4 Hz, 2H); 7.23-7.39 (m, ~40H); 7.17 (br.m, 2H); 7.16 (d, J = 8.6 Hz, 2H);
δ
7
7
.04 (d, J = 8.6 Hz, 2H); 6.86 (d, J = 8.4 Hz, 2H); 4.97 (d, J = 13.7 Hz, 2H); 4.42 (d, J = 13.6 Hz, 4H); 3.73
+
(
br.d, J = 13.6 Hz, 2H) ppm. HRMS (ESI) calculated for C H N [M - Br] : 1210.5347, found 1210.5327.
94
68
(
S)-2’,6’-Bis(4-tritylphenyl)-3’,5,5’,7-tetrahydrospiro[dibenzo[c,e]azepine-6,4’-dinaphtho[2,1-c:1’,2’-
◦
20
1
e]azepin]-6-ium bromide (1e’): 66% yield; mp: 260–270 C (dec.), [
α
]D = -130 (c: 0.68, DCM). H-NMR
: 8.12 (s, 2H); 8.04 (d, J = 8.3 Hz, 2H); 7.81 (d, J = 7.6 Hz, 2H); 7.63 (t, J = 7.5 Hz, 2H); 7.51–7.56 (m, 4H);
.46 (t, J = 7.5 Hz, 2H); 7.15–7.45 (br.m, ~12H); 7.10–7.18 (m, ~16H); 7.07 (dm, J = 8.6 Hz, 4H); 6.95 (dm,
δ
7
J = 7.6 Hz, 10H); 4.85 (d, J = 13.3 Hz, 2H); 4.65 (d, J = 13.3 Hz, 2H); 4.48 (d, J = 12.8 Hz, 2H); 2.76 (d,
J = 12.8 Hz, 2H) ppm. 13C-NMR
: 146.55 (C); 146.23 (C); 140.52 (C); 139.01 (C); 138.47 (C); 136.52 (C);
34.30 (C); 131.85 (CH); 131.16 (CH); 131.10 (C); 131.08 (CH); 130.96 (CH); 130.86 (CH); 128.98 (CH);
28.84 (CH); 128.03 (CH); 127.77 (CH); 127.45 (CH); 127.17 (CH); 127.07 (C); 126.01 (CH); 124.35 (C);
δ
1
1
6
+
4.52 (C); 62.62 (CH ); 59.23 (CH ) ppm. HRMS (ESI) calculated for C H N [M
−
Br] : 1110.5033,
2
2
86 64
found 1110.5033.
(
S,S)-2,6-Bis(4-fluorophenyl)-3,3’,5,5’-tetrahydro-4,4’-spirobi[dinaphtho[2,1-c:1’,2’-e]azepin]-4-ium
1
bromide (1f) [25]: 50% yield. H-NMR
δ: 8.28 (s, 2H); 8.08 (d, J = 8.2 Hz, 2H); 7.87 (d, J = 8.2 Hz, 2H);
7
.59 (ddd, J = 8.0, 6.7, 1.1 Hz, 2H); 7.49 (ddd, J = 8.1, 6.7, 1.2 Hz, 2H); 7.41 (d, J = 8.3 Hz, 2H); 7.28 (ddd,
J = 8.2, 6.7, 1.2 Hz, 2H); 7.19 (ddd, J = 8.2, 6.7, 1.1 Hz, 2H); 7.10 (dd, J = 9.0, 0.9 Hz, 2H); 7.08 (dd, J = 8.6,
.9 Hz, 2H); 6.33 (d, J = 8.5 Hz, 2H); 4.93 (d, J = 14.0 Hz, 2H); 4.42 (dd, J = 14.0, 1.4 Hz, 2H); 4.24 (d,
J = 13.6 Hz, 2H); 3.72 (dd, J = 13.5, 1.1 Hz, 2H) ppm; Note: in addition a broad band was observed
7.3–8.5 ppm) corresponding to ~8H. 13C-NMR
: 163.25 (d, JCF = 249.5 Hz, C); 139.31 (C); 138.05 (C);
36.32 (C); 135.50 (d, JCF = 3.5 Hz, C); 133.92 (C); 132.85 (br.d, JCF = 6.6 Hz, CH); 132.56 (CH); 131.11 (d,
JCF = 9.4 Hz, C); 128.70 (CH); 128.49 (CH); 128.37 (CH); 128.28 (CH); 127.54 (CH); 127.52 (CH); 127.41
0
(
1
δ
(
(
CH); 126.84 (CH); 126.67 (CH); 124.91 (C); 122.48 (C); 117.04 (d, JCF = 21.7 Hz, CH); 62.46 (CH ); 57.42
2
+
CH ) ppm. HRMS (ESI) calculated for C H F N [M − Br] : 762.2967, found 762.2951.
2
56 38 2
(
11bS,11b’S)-2,6-Bis(3,4,5-trifluorophenyl)-3,3’,5,5’-tetrahydro-4,4’-spirobi[dinaphtho[2,1-c:1’,2’-
1
e]azepin]-4-ium bromide (1g) [25]: 66% yield. H-NMR
δ
: 8.26 (s, 2H); 8.09 (d, J = 8.2 Hz, 2H); 7.93 (d,
J = 8.2 Hz, 2H); 7.63 (ddd, J = 8.0, 6.8, 1.1 Hz, 2H); 7.54 (ddd, J = 8.2, 6.8, 1.2 Hz, 2H); 7.53 (d, J = 8.7 Hz,
H); 7.33 (ddd, J = 8.4, 6.8, 1.2 Hz, 2H); 7.25 (ddd, J = 8.2, 6.7, 1.2 Hz, 2H); 7.13 (d, J = 8.7 Hz, 2H); 7.09
d, J = 8.7 Hz, 2H); 6.53 (d, J = 8.4 Hz, 2H); 4.81 (d, J = 14.0 Hz, 2H); 4.64 (d, J = 14.0 Hz, 2H); 4.45 (d,
J = 13.8 Hz, 2H); 3.73 (d, J = 13.7 Hz, 2H) ppm. 13C-NMR
: 151.98 (dm, JCF = 251 Hz, C); 140.29 (dt,
JCF = 257, 15.2 Hz, C); 139.54 (C); 136.65 (C); 136.24 (C); 135.73 (m, C); 134.16 (C); 133.80 (C); 132.99
2
(
δ
(
(
(
CH); 131.62 (C); 131.26 (C); 128.72 (CH); 128.67 (CH); 128.53 (CH); 128.39 (CH); 128.16 (CH); 127.83
CH); 127.50 (CH); 127.47 (CH); 127.20 (CH); 126.60 (CH); 124.85 (C); 122.11 (C); 115.35 (m, CH); 62.62
+
CH ); 57.31 (CH ) ppm. HRMS (ESI) calculated for C H F N [M − Br] : 834.2590, found 834.2595.
2
2
56 34 6
(
S,S)-2,6-Bis(3,5-bis(trifluoromethyl)phenyl)-3,3’,5,5’-tetrahydro-4,4’-spirobi[dinaphtho[2,1-c:1’,2’-
1
e]azepin]-4-ium bromide (1h) [47]: 62% yield. H-NMR
δ
: ~8.4–9.4 (br.s, ~2H); 8.33 (s, 2H); 8.25 (s, 2H);
8
.16 (d, J = 8.3 Hz, 2H); 7.84 (d, J = 8.3 Hz, 2H); 7.69 (ps.t, J = 7.3 Hz, 2H); 7.51 (ps.t, J = 7.7 Hz, 2H); 7.41
(
(
br.ddd, J = 8.3, 6.8, 1.0 Hz, 2H); 7.24 (d, J = 8.9 Hz, 2H); 7.23 (br.ddd, J = 7.9, 6.6, 1.0 Hz, 2H); 7.19
d, J = 8.7 Hz, 2H); 7.08 (d, J = 8.5 Hz, 2H); 6.24 (d, J = 8.7 Hz, 2H); 4.83 (d, J = 13.9 Hz, 2H); 4.64 (d,
J = 14.1 Hz, 2H); 4.54 (d, J = 13.9 Hz, 2H); 3.67 (d, J = 13.7 Hz, 2H) ppm. 13C-NMR
δ
: 141.96 (C); 139.76
C); 136.52 (C); 136.06 (C); 134.00 (CH); 133.92 (C); 133.90 (C); 131.94 (C); 131.11 (C); 128.97 (CH); 128.80
CH); 128.58 (CH); 128.54 (CH); 128.24 (CH); 127.86 (CH); 127.63 (CH); 127.42 (CH); 127.24 (CH); 125.91
CH); 124.38 (C); 122.35 (br.CH); 121.76 (C); 62.77 (CH ); 57.45 (CH ) ppm. HRMS (ESI) calculated for
(
(
(
2
2
+
C H F N [M − Br] : 998.2651, found 998.2644.
60
36 12
(
S,S)-2,6-Di(furan-2-yl)-3,3’,5,5’-tetrahydro-4,4’-spirobi[dinaphtho[2,1-c:1’,2’-e]azepin]-4-ium bromide
◦
20
1
(1i): 81% yield; mp: >200 C (dec.), [α]D = +288 (c: 0.58, DCM). H-NMR δ: 8.50 (s, 2H); 8.11 (d,