Molecules 2018, 23, 226
9 of 12
1
[
-Ethyl-2-((E)-2-((E)-6-(2-((E)-1-ethyl-5-methoxy-3,3-dimethylindolin-2-ylidene)ethylidene)-3,4,5,6-tetrahydro-
0 ◦
1,1 -biphenyl]-2-yl)vinyl)-5-methoxy-3,3-dimethyl-3H-indol-1-iumiodide, 6i; Yield 61%; m.p. > 260 C;
1
H NMR (acetone-d6)
δ
1.22 (s; 12H), 1.34 (t, J = 7.2 Hz, 6H), 2.02 (m, 2H), 2.73 (t, J = 6.0 Hz, 4H),
.84 (s, 6H), 4.21 (m, 4H), 6.23 (d, J = 14 Hz, 2H), 6.23 (d, J = 2.8 Hz, 2H) 6.94 (d, J = 2.4 Hz 2H)
.22 (s, 2H) 7.28 (m, 6H) 7.66 (m, 3H); 13C NMR (acetone-d6)
11.6, 21.3 24.5, 26.8, 39.0, 48.8, 55.4, 99.1,
3
7
δ
1
09.0, 111.2, 113.4, 128.0, 128.7, 129.5, 130.3, 135.5, 139.4, 142.8, 145.0, 158.1, 161.0, 170.6. HRMS (ESI)
+
m/z: calcd. for C H N O 613.3789, obsd 613.3777.
42
49
2
2
3
-Ethyl-2-((E)-2-((E)-6-((E)-2-(3-ethyl-1,1-dimethyl-1,3-dihydro-2H-benzo[e]indol-2-ylidene)ethylidene)-3,4,5,6
0
-tetrahydro-[1,1 -biphenyl]-2-yl)vinyl)-1,1-dimethyl-1H-benzo[e]indol-3-ium iodide, 6j
;
Yield 65%;
◦
1
m.p. > 260 C; H NMR (CDCl )
2
δ 1.46 (t, J = 6.8 Hz, 6H), 1.51 (s, 12H), 2.13 (t, J = 5.6 Hz, 2H),
3
13
.79 (t, J = 6.0 Hz, 4H), 4.28 (m, 4H), 6.17 (d, J = 14.0 Hz, 2H), 7.45 (m, 13H), 7.94 (m, 6H); C NMR
(
1
CDCl3)
δ
99.3, 110.4, 122.0, 124.8, 127.6, 128.1, 128.3, 128.7, 129.5, 130.1, 130.7, 131.7, 132.0, 133.3, 139.1,
+
39.3, 147.3, 162.0, 172.4. HRMS (ESI) m/z: calcd. for C H Cl N 593.2485, obsd 593.2475.
48
49
2
2
0
,3,3-Trimethyl-2-((E)-2-((E)-6-(2-((E)-1,3,3-trimethylindolin-2-ylidene)ethylidene)-3,4,5,6-tetrahydro-[1,1 -biphenyl]
1
-
◦
2-yl)vinyl)-3H-indol-1-ium iodide, 6k; yield 68%; m.p. > 260 C; H-NMR (CDCl ) δ 1.04 (t, J = 7.2 Hz,
3
1
6H), 1.23 (s, 12H), 1.49 (m, 4H), 1.80 (m, 4H), 2.11 (t, J = 6.0 Hz, 2H), 2.745 (s, 4H), 4.04 (t, J = 7.2 Hz,
4
H), 6.10 (d, J = 14 Hz, 2H), 7.07 (d, J = 11.6 Hz, 2H), 7.22 (m, 6H), 7.33 (t, J = 7.2 Hz, 2H), 7.61 (m, 3H);
13
C NMR (CDCl ) 14.0, 20.5, 21.3, 25.0, 27.7, 29.4, 110.4, 122.1, 124.8, 128.2, 128.6, 129.6, 140.8, 142.3.
3
+
HRMS (ESI) m/z: calcd. for C H N 609.4203, obsd 609.4198.
44
53
2
1
-Butyl-2-((E)-2-((E)-6-(2-((E)-1-butyl-5-chloro-3,3-dimethylindolin-2-ylidene)ethylidene)-3,4,5,6-tetra-hydro-
0
1
[
(
2
1,1 -biphenyl]-2-yl)vinyl)-5-chloro-3,3-dimethyl-3H-indol-1-ium iodide, 6l: Yield 67%; m.p. > 260; H NMR
CDCl3) 1.03 (t, J = 7.2 Hz, 6H), 1.191 (s, 12H), 1.47 (m, 4H), 1.78 (t, J = 6.8 Hz, 4H), 2.12 (s, 2H),
.75 (s, 4H), 4.02 (s, 4H), 6.09 (d, J = 12.4 Hz, 2H), 6.98 (d, J = 8.0 Hz, 2H), 7.28 (m, 8H), 7.86 (m, 3H); 13
14.0, 20.4, 21.3, 25.0, 27.7, 29.3, 44.7, 48.6, 100.4, 111.3, 122.7, 128.3, 128.6, 129.6, 130.2,
δ
C
NMR (CDCl3)
δ
+
1
38.7, 141.0, 142.4, 148.5, 171.0. HRMS (ESI) m/z: calcd. for C H Cl N 677.3424, obsd 677.3421.
44 51 2 2
0
-Butyl-2-((E)-2-((E)-6-(2-((E)-1-butyl-3,3-dimethylindolin-2-ylidene)ethylidene)-3,4,5,6-tetrahydro-[1,1 -biphenyl]
1
-
◦
1
2-yl)vinyl)-3,3-dimethyl-3H-indol-1-ium iodide, 6m: Yield 65%; m.p. > 260 C; H NMR (CDCl ),
δ
3
1
.04 (t, J = 7.2 Hz, 6H), 1.20 (s, 12H), 1.51 (m, 4H), 1.81 (m, 4H), 2.13 (t, J = 5.2 Hz, 2H), 2.75 (s, 4H),
4
.04 (t, J =7.2 Hz, 4H), 6.10 (d, J = 14.0 Hz, 2H), 7.07 (d, J = 8 Hz, 2H), 7.20 (m, 8H), 7.61 (m, 3H);
13
C NMR (CDCl3)
δ
14.0, 20.5, 21.3, 25.0, 27.7, 29.4, 44.4, 48.6, 100.0, 110.3, 122.1, 124.7, 128.2, 128.6,
+
129.6, 132.1, 138.8, 140.8, 142.3, 148.4, 162.9, 171.4. HRMS (ESI) m/z: calcd. for C H Br N 765.2414,
44
51
2
2
obsd 765.2422.
1
-Butyl-2-((E)-2-((E)-6-(2-((E)-1-butyl-5-methoxy-3,3-dimethylindolin-2-ylidene)ethylidene)-3,4,5,6-tetrahydro
0
◦
-
[1,1 -biphenyl]-2-yl)vinyl)-5-methoxy-3,3-dimethyl-3H-indol-1-ium iodide, 6n: Yield 66%; m.p. > 260 C;
H NMR (CDCl3)
1
δ
1.01 (t, J = 6.8 Hz, 6H), 1.17 (s, 12H), 1.46 (m, 4H), 1.80 (m, 4H), 2.07 (s, 2H),
.68 (s, 4H), 3.82 (s, 6H), 4.03 (t, J = 7.2 Hz, 4H), 6.00 (d, J = 14.0 Hz, 2H) 6.78 (s, 2H), 6.88 (d, J = 8.4 Hz,
H), 7.03 (d, J = 8.8 Hz, 2H), 7.11 (d, J = 14.0 Hz, 2H), 7.21 (d, J = 6.8 Hz, 2H), 7.57 (m, 3H); 13C NMR
2
2
(
1
CDCl3)
δ
13.9, 20.4, 21.3, 24.8, 27.7, 29.4, 44.6, 48.7, 56.0, 99.4, 109.1, 111.1, 113.1, 128.1, 128.6, 129.4,
+
30.9, 135.9, 139.0, 142.4, 146.9, 157.9, 161.4, 170.6. HRMS (ESI) m/z: calcd. for C H N O 669.4415,
46
57
2
2
obsd 669.4404.
3
6
-Butyl-2-((E)-2-((E)-6-((E)-2-(3-butyl-1,1-dimethyl-1,3-dihydro-2H-benzo[e]indol-2-ylidene)ethylidene)-3,4,5,
0
-tetrahydro-[1,1 -biphenyl]-2-yl)vinyl)-1,1-dimethyl-1H-benzo[e]indol-3-ium iodide, 6o
:
Yield 70%;
1.03 (t, J = 7.2 Hz, 6H), 1.52 (m, 16H), 1.86 (m, 4H), 2.16 (t, J = 6.0 Hz,
H), 2.79 (s, 4H), 4.17 (s, 4H), 6.15 (d, J = 14.4 Hz, 2H), 7.34 (m, 6H), 7.45 (d, J = 7.6 Hz, 2H), 7.53 (m,
H), 7.68 (t, J = 2.8 Hz, 3H), 7.93 (m, 6H); 13C NMR (CDCl3)
14.0, 20.4, 21.4, 25.0, 27.2, 29.7, 44.6, 50.4,
◦
1
m.p. >260 C; H NMR (CDCl )
2
2
δ
3
δ