R. Neumann et al.
FULL PAPER __________________________________________________________________________
1
Table 6 H and 13C NMR data of propyne iminium triflates 5a–n
Com-
pound
1H NMR a)
13C NMR b)
5a
2.37 (quin, 2H), 3.39 (t, 2H), 4.22 (t, 2H), 4.66 (d, 2H),
5.51 (dd, 3J = 10.2 Hz, 2J = 1.0 Hz, 1H), 5.57 ( dd, 3J =
17.1 Hz, 2J = 1.0 Hz, 1H), 5.98 (mc, 1H), 7.56/7.78 (AA'
BB', 4H)
20.1 (t), 40.9 (t), 56.1 (t), 59.7 (t), 79.5 (s), 116.7 (s), 117.7 (s), 122.2
(q, JC,F = 321.1 Hz), 123.7 (t), 128.9 (d), 130.7 (d, 2C), 136.3 (d, 2C),
140.3 (s), 169.4 (s)
5b
2.35 (quin, 2H), 3.35 (t, 2H), 4.18 (t, 2H), 4.59 (d, 2H),
5.49 (dd, 3J = 10.2 Hz, 2J = 1.0 Hz, 1H), 5.55 (dd, 3J = 17.1
Hz, 2J = 1.0 Hz, 1H), 5.97 (mc, 1H), 7.28 (dd, 3J = 5.0 Hz,
3J = 3.8 Hz, 1H), 7.86 (dd, 3J = 3.8 Hz, 4J = 1.2 Hz, 1H),
7.99 (dd, 3J = 5.0 Hz, 4J = 1.2 Hz, 1H)
20.3 ( t), 40.6 (t), 55.8 (t), 59.5 (t), 84.2 (s), 112.9 (s), 118.4 (s), 123.5
(t), 129.1 (d), 130.2 (d), 138.4 (d), 141.7 (d), 168.5 (s) c)
5c
2.27 (quin, 2H), 3.36 (t, 2H), 4.07 (t, 2H), 5.17 (s, 2H),
7.28 (dd, 3J = 5.0 Hz, 3J = 3.9 Hz, 1H), 7.46 (m, 5H), 7.88
(dd, 3J = 3.9 Hz, 4J = 1.0 Hz, 1H), 7.99 (dd, 3J = 5.0 Hz,
4J = 0.6 Hz, 1H)
20.2 (t), 40.6 (t), 57.2 (t), 59.4 (t), 84.5 (s), 113.3 (s), 118.0 (s), 122.1
(q, JC,F = 320.3 Hz), 130.2 (d), 130.3 (4 d), 130.5 (d), 132.3 (s), 138.6
(d), 141.9 (d), 168.6 (s)
5d
5e
1.83–1.90 (m, 2H), 1.97–2.04 (m, 2H), 3.10 (mc, 2H),
3.83 (mc, 2H), 4.74 (d, 2H), 5.49–5.59 (m, 2H), 6.01
(mc, 1H), 7.55/7.73 (AA'BB', 4H)
17.4 (t), 21.3 (t), 35.0 (t), 53.2 (t), 63.1 (t), 83.3 (s), 113.7 (s), 117.9 (s),
121.8 (q, JC,F = 320.3 Hz), 123.3 (t), 129.2 (d), 130.6 (d, 2C), 136.1 (d,
2 C), 139.9 (s), 167.9 (s)
1.80–2.04 (m, 4H), 3.06 (mc, 2H), 3.80 (mc, 2H), 4.69
(d, 2H), 5.47–5.57 (m, 2H), 5.99 (mc, 1H), 7.39 (dd,
3J = 5.1 Hz, 4J = 1.1 Hz, 1H), 7.60 (dd, 3J = 5.1 Hz, 4J =
2.9 Hz, 1H), 8.23 (dd, 4J = 2.9 Hz, 4J = 1.1 Hz, 1H)
1.81–1.87 (m, 2H), 1.92–2.02 (m, 2H), 3.06 (mc, 2H),
3.80 (mc, 2H), 4.66 (d, 2H), 5.47–5.56 (m, 2H), 5.99
(mc, 1H), 7.26 (dd, 3J = 5.1 Hz, 3J = 3.8 Hz, 1H), 7.81
(dd, 3J = 5.1 Hz, 4J = 1.2 Hz, 1H), 7.95 (dd, 3J = 3.8 Hz,
4J = 1.2 Hz, 1H)
17.5 (t), 21.3 (t), 34.9 (t), 53.0 (t), 62.8 (t), 83.2 (s), 111.2 (s), 118.5 (s),
123.2 (t), 129.1 (d), 129.3 (d), 131.1 (d), 139.4 (d), 167.8 (s) c)
5f
18.1 (t), 22.0 (t), 35.2 (t), 53.6 (t), 63.5 (t), 88.3 (s), 110.5 (s), 119.1 (s),
122.8 (q, JC,F = 321.2 Hz), 123.7 (t), 129.9 (d), 130.7 (d), 138.3 (d),
141.7 (s), 167.7 (s)
5g
1.77–1.86 (m, 2H), 1.90–2.00 (m, 2H), 2.63 (q, 2H),
3.05 (mc, 2H), 3.83 (mc, 2H), 4.15 (t, 2H), 5.16 (d, 3J =
10.2 Hz, 1H), 5.23 (d, 3J = 17.1 Hz, 1H), 5.87 (mc, 1H),
7.55/7.71 (AA'BB', 4 H)
17.4 (t), 21.2 (t), 32.2 (t), 34.8 (t), 53.6 (t), 60.3 (t), 83.3 (s), 113.6 (s),
118.0 (s), 119.6 (t), 130.6 (d, 2C), 134.0 (d), 136.0 (d, 2C), 139.9 (s),
167.5 (s), c)
5h
5i
1.82–1.85 (m, 2H), 1.90–1.95 (m, 2H), 3.15 (t, 2H),
3.71–3.74 (m, 2H), 5.31 (s, 2H), 7.47 (s, br, 4H),
7.54/7.73 (AA'BB', 4H)
1.80–1.85 (m, 2H), 1.90–1.94 (m, 2H), 3.12 (t, 2H),
3.71 (m, 2H), 5.28 (s, 2H), 7.39 (dd, 1H), 7.45–7.49
(m, 4H), 7.59 (dd, 1H), 8.23 (dd, 1H)
17.4 (t), 21.3 (t), 35.4 (t), 53.1 (t), 63.3 (t), 83.7 (s), 114.3 (s), 117.8 (s),
122.2 (q), 130.3 (d, 2C), 130.6 (d, 2C), 131.4 (s), 131.8 (d, 2C), 135.9
(s), 136.2 (d, 2C), 140.2 (s), 168.6 (s)
17.5 (t), 21.3 (t), 35.2 (t), 53.0 (t), 63.1 (t), 83.7 (s), 111.9 (s), 118.3 (s),
122.2 (q), 129.2 (d), 130.3 (d, 2C), 131.1 (d), 131.6 (s), 131.8 (d, 2C),
136.0 (s), 139.8 (d), 168.5 (s)
5j
1.81–1.85 (m, 2H), 1.90–1.94 (m, 2H), 3.12 (t, 2H),
3.73 (t, 2H), 5.25 (s, 2H), 7.24 (dd, 3J = 5.1 Hz, 3J =
3.8 Hz, 1H), 7.46 (s, br, 4H), 7.80 (dd, 3J = 3.8 Hz, 4J =
1.1 Hz, 1H), 7.94 (dd, 3J = 5.1 Hz, 4J = 1.1 Hz, 1H)
1.82–1.87 (m, 2H), 1.91–1.95 (m, 2H), 3.17 (t, 2H),
3.75 (m, 2H), 5.36 (s, 2H), 7.42–7.50 (m, 5H). 7.51/7.72
(AA'BB', 4H)
1.81–1.86 (m, 2H), 1.91–1.96 (m, 2H), 3.12 (t, 2H), 3.75
(t, 2H), 5.28 (s, 2H), 7.25 (dd, 3J = 5.1 Hz, 3J = 3.8 Hz,
1H), 7.45–7.48 (m, 5H), 7.81 (dd, 3J = 3.8 Hz, 4J = 0.9 Hz,
1H), 7.94 (dd, 3J = 5.1 Hz, 4J = 0.9 Hz, 1H)
17.5 (t), 21.4 (t), 34.9 (t), 53.1 (t), 63.1 (t), 88.2 (s), 110.6 (s), 118.3 (s),
122.2 (q), 130.1 (d), 130.3 (d, 2C), 131.7 (d, 2C), 131.7 (s), 135.8 (s),
138.1 (d), 141.4 (d), 167.8 (s)
5k
5l
17.5 (t), 21.3 (t), 35.3 (t), 53.1 (t), 64.1 (t), 83.8 (s), 113.8 (s), 117.8 (s),
122.2 (q), 129.9 (d, 2C), 130.3 (d, 2C), 130.4 (d), 130.5 (d, 2C), 132.6
(s), 136.1 (d, 2C), 139.9 (s) 168.2 (s)
17.5 (t), 21.4 (t), 34.8 (t), 53.0 (t), 63.9 (t), 88.2 (s), 110.2 (s), 118.3 (s),
122.2 (q), 129.9 (d, 2C), 130.1 (d), 130.3 (d, 2C), 130.4 (d), 132.9 (s),
138.0 (d), 141.3 (d), 167.4 (s)
5m
5n
1.73–1.91 (m, 6H), 3.23 (mc, 2H), 4.08 (mc, 2H), 4.78
(d, 2H), 5.50 (d, 3J = 10.3 Hz, 1H), 5.57 (d, 3J = 17.0 Hz,
1H), 5.98 (mc, 1H), 7.53/7.74 (AA'BB', 4H)
1.58–1.88 (m, 6H), 3.18 (mc, 2H); 4.05 (mc, 2H), 4.71
(d, 2H), 5.47 (dd, 3J = 10.2 Hz, 2J = 0.9 Hz, 1H), 5.54
(dd, 3J = 17.1 Hz, 2J = 1.0 Hz, 1H), 5.95 (mc, 1H), 7.26
(dd, 3J = 5.0 Hz, 3J = 3.8 Hz, 1H), 7.85 (dd, 3J = 3.8 Hz,
4J = 1.1 Hz, 1H), 8.00 (dd, 3J = 5.0 Hz, 4J = 1.1 Hz, 1H)
22.5 (t), 24.8 (t), 29.5 (t), 38.7 (t), 57.4 (t), 64.6 (t), 85.4 (s), 117.0 (s),
117.9 (s), 122.2 (q, JC,F = 320.7 Hz), 123.9 (t), 129.0 (d), 130.6 (d, 2C),
136.4 (d, 2C), 140.3 (s), 172.5 (s)
22.8 (t), 25.0 (t), 29.6 (t), 38.3 (t), 57.2 (t), 64.3 (t), 90.1 (s), 113.2 (s),
118.6 (s), 123.6 (t), 129.2 (d), 130.3 (d), 138.8 (d), 141.9 (s), 171.4 (s) c)
a) CD3CN as solvent, 500.14 MHz, δ values in ppm. b) Solvent CD3CN, 125.77 MHz, δ values in ppm; signal multiplicities of proton-coupled spectra are given
in parentheses. c) CF3SO3– not found.
tals; yield 3.11 g (79%). – IR (KBr): ν/cm–1 = 3060 (w), 2968
(w), 2207 (s), 1648 (s), 1586 (s) 1461 (m), 1387 (s), 1276
(vs), 1174 (s), 1100 (m), 1090 (s), 1030 (vs).
(–60 °C) solution of triflic anhydride (5.54 ml, 33 mmol) in
CH2Cl2 (100 ml). After removing the solvent in vacuo, the
dark oil was dissolved in CH3CN and placed in a thick-walled
Schlenk tube. After 15 minutes at 60 °C, the elimination of
HOTf was complete. The solution was concentrated to half
its volume, and diethyl ether was added. After stirring at
0 °C, 5b could be isolated as a dark solid which was triturated
with diethyl ether (3×50 ml), then dissolved in CH3CN and
precipitated with diethyl ether to give a yellow powder; yield
8.44 g (77%). – IR (KBr): ν/cm–1 = 3071 (w), 2189 (s), 1628
Synthesis of Propyne Iminium Triflates 5b,f
1-Allyl-5-[2-(2-thienyl)-1-ethynyl]-3,4-dihydro-2H-pyrro-
lium Trifluoromethanesulfonate (5b); Typical Procedure
A solution of enaminoketone 3b (7.0 g, 30 mmol) in CH2Cl2
(50 ml) was added dropwise during 20 min to a cooled
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J. Prakt. Chem. 1999, 341, No. 2