H
R. Blieck et al.
Paper
Synthesis
1H NMR (300 MHz, CDCl3): = 6.66 (dt, J = 14.2, 1.2 Hz, 1 H), 5.94–
5.74 (m, 1 H), 5.36–5.22 (m, 2 H), 4.92 (dt, J = 14.3, 7.2 Hz, 1 H), 4.16
(dt, J = 5.4, 1.6 Hz, 2 H), 3.74–3.66 (m, 4 H), 2.98 (dd, J = 7.2, 1.2 Hz, 2
H), 2.91 (s, 3 H), 2.46–2.39 (m, 4 H).
HRMS (ESI): m/z [M + H]+ calcd for C18H27N2O2S: 335.1793; found:
335.1793.
(E)-N-Allyl-N-[3-(4-methylpiperazin-1-yl)prop-1-enyl]-p-toluene-
sulfonamide (2r)
13C NMR (75 MHz, CDCl3): = 131.4, 128.9, 118.7, 106.3, 67.1, 59.2,
53.4, 48.2, 40.2.
The reaction of N-allenyl-N-allyl-p-toluenesulfonamide (1b; 125 mg,
0.50 mmol) with N-methylpiperazine (66 L, 0.6 mmol, 1.2 equiv) ac-
cording to the general procedure (reaction time: 18 h, flash chroma-
tography: CH2Cl2/MeOH 99:1) gave 2r (155 mg, 89%) as an orange oil.
HRMS (EI): m/z [M]+ calcd for C11H20N2O3S: 260.1195; found:
260.1189.
1H NMR (400 MHz, CDCl3): = 7.68–7.59 (m, 2 H), 7.28 (d, J = 8.0 Hz, 2
H), 6.78 (d, J = 14.2 Hz, 1 H), 5.61 (ddt, J = 17.2, 10.5, 5.3 Hz, 1 H),
5.22–5.07 (m, 2 H), 4.81 (dt, J = 14.3, 7.2 Hz, 1 H), 3.99 (dt, J = 5.2, 1.5
Hz, 2 H), 2.99 (dd, J = 7.2, 0.9 Hz, 2 H), 2.47 (s, 8 H), 2.41 (s, 3 H), 2.31
(s, 3 H).
(E)-N-Allyl-N-[3-(diethylamino)prop-1-enyl]-p-toluenesulfon-
amide (2o)
The reaction of N-allenyl-N-allyl-p-toluenesulfonamide (1b; 74.8 mg,
0.30 mmol) with diethylamine (37.2 L, 0.36 mmol, 1.2 equiv) ac-
cording to the general procedure (reaction time: 18 h, flash chroma-
tography: EtOAc) gave 2o (79.3 mg, 82%) as a pale brown oil.
13C NMR (101 MHz, CDCl3): = 144.0, 136.3, 131.6, 129.9, 129.4,
127.1, 118.1, 106.7, 58.7, 54.9, 52.4, 48.2, 45.9, 21.7.
IR (ATR): 2969, 2929, 2809, 1656, 1613, 1354, 1164, 844, 813, 664 cm–1
.
Due to the limited stability of this compound in the analysis condi-
tions, no meaningful HRMS data (either EI or ESI) could be obtained.
However, comparison of spectral data with analogous compounds
that could be fully characterized allowed establishing the structure
beyond reasonable doubt.
1H NMR (300 MHz, CDCl3): = 7.64 (d, J = 8.3 Hz, 2 H), 7.28 (d, J = 8.3
Hz, 2 H), 6.75 (dt, J = 14.2, 1.2 Hz, 1 H), 5.62 (ddt, J = 17.3, 10.4, 5.4 Hz,
1 H), 5.21–5.08 (m, 2 H), 4.82 (dt, J = 14.2, 7.1 Hz, 1 H), 3.98 (dt, J = 5.4,
1.7 Hz, 2 H), 3.06 (dd, J = 7.1, 1.2 Hz, 2 H), 2.45 (q, J = 7.2 Hz, 4 H), 2.40
(s, 3 H), 0.99 (t, J = 7.2 Hz, 6 H).
13C NMR (75 MHz, CDCl3): = 143.9, 136.4, 131.7, 129.8, 128.4, 127.1,
117.9, 108.2, 53.2, 48.2, 46.3, 21.6, 11.7.
HRMS (EI): m/z [M]+ calcd for C17H26N2O2S: 322.1715; found:
322.1708.
(E)-N-Allyl-N-[3-(azepan-1-yl)prop-1-enyl]-p-toluenesulfon-
amide (2s)
The reaction of N-allenyl-N-allyl-p-toluenesulfonamide (1b; 125 mg,
0.50 mmol) with azepane (68 L, 0.6 mmol, 1.2 equiv) according to
the general procedure (reaction time: 18 h, flash chromatography:
CH2Cl2/MeOH 98:2) gave 2s (132 mg, 76%) as an orange oil.
1H NMR (400 MHz, CDCl3): = 7.69–7.62 (m, 2 H), 7.29 (d, J = 8.0 Hz, 2
H), 6.76 (d, J = 14.2 Hz, 1 H), 5.62 (ddt, J = 17.2, 10.5, 5.3 Hz, 1 H),
5.25–5.08 (m, 2 H), 4.88 (dt, J = 14.2, 7.1 Hz, 1 H), 3.99 (dt, J = 5.3, 1.5
Hz, 2 H), 3.12 (d, J = 7.0 Hz, 2 H), 2.60 (br s, 4 H), 2.42 (s, 3 H), 1.70–
1.54 (m, 8 H).
13C NMR (101 MHz, CDCl3): = 144.0, 136.3, 131.6, 129.9, 127.1,
118.1, 95.1, 58.7, 55.1, 48.2, 27.6, 27.0, 21.7.
HRMS (ESI): m/z [M + H]+ calcd for C19H29N2O2S: 349.1950; found:
349.1946.
(E)-N-Allyl-N-{3-[butyl(methyl)amino]prop-1-enyl}-p-toluenesul-
fonamide (2p)
The reaction of N-allenyl-N-allyl-p-toluenesulfonamide (1b; 125 mg,
0.50 mmol) with N-methylbutylamine (71 L, 0.6 mmol, 1.2 equiv)
according to the general procedure (reaction time: 18 h, flash chro-
matography: petroleum ether/EtOAc gradient 90:10 to 100:0) gave 2p
(138 mg, 82%) as a red oil.
1H NMR (400 MHz, CDCl3): = 7.69–7.62 (m, 2 H), 7.28 (d, J = 8.0 Hz, 2
H), 6.76 (d, J = 14.2 Hz, 1 H), 5.63 (ddt, J = 17.2, 10.5, 5.3 Hz, 1 H),
5.20–5.12 (m, 2 H), 4.83 (dt, J = 14.2, 7.1 Hz, 1 H), 3.99 (d, J = 5.2 Hz, 2
H), 2.96 (d, J = 7.0 Hz, 2 H), 2.41 (s, 3 H), 2.32–2.22 (m, 2 H), 2.15 (s, 3
H), 1.48–1.36 (m, 2 H), 1.35–1.20 (m, 2 H), 0.89 (t, J = 7.3 Hz, 3 H).
(E)-N-Allyl-N-[3-(2-methylpiperidin-1-yl)prop-1-enyl]-p-toluene-
sulfonamide (2t)
13C NMR (101 MHz, CDCl3): = 143.9, 136.4, 131.7, 129.9, 128.6,
127.1, 118.0, 108.3, 58.1, 56.8, 48.2, 41.9, 29.6, 21.7, 20.9, 14.2.
The reaction of N-allenyl-N-allyl-p-toluenesulfonamide (1b; 74.8 mg,
0.30 mmol) with 2-methylpiperidine (42.3 L, 0.36 mmol, 1.2 equiv)
according to the general procedure (flash chromatography: EtOAc/pe-
troleum ether 85:15) gave 2t (79.5 mg, 76%) as a pale brown oil.
HRMS (ESI): m/z [M + H]+ calcd for C18H29N2O2S: 337.1950; found:
337.1948.
(E)-N-Allyl-N-[3-(piperidin-1-yl)prop-1-enyl]-p-toluenesulfon-
amide (2q)
IR (ATR): 2928, 2856, 2791, 1654, 1598, 1355, 1306, 1163, 1090,
664 cm–1
.
The reaction of N-allenyl-N-allyl-p-toluenesulfonamide (1b; 74.8 mg,
0.30 mmol) with piperidine (35.6 L, 0.36 mmol, 1.2 equiv) according
to the general procedure (flash chromatography: EtOAc/petroleum
ether 85:15) gave 2q (85.3 mg, 85%) as a pale brown oil.
1H NMR (300 MHz, CDCl3): = 7.65 (d, J = 8.3 Hz, 2 H), 7.29 (d, J = 8.3
Hz, 2 H), 6.74 (dt, J = 14.0, 1.0 Hz, 1 H), 5.63 (ddt, J = 17.3, 10.4, 5.3 Hz,
1 H), 5.23–5.10 (m, 2 H), 4.85 (ddd, J = 14.2, 8.2, 6.2 Hz, 1 H), 4.10–
3.89 (m, 2 H), 3.36 (ddd, J = 14.0, 6.2, 1.0 Hz, 1 H), 2.96 (ddd, J = 14.0,
8.2, 1.0 Hz, 1 H), 2.78 (ddd, J = 11.3, 4.6, 3.3 Hz, 1 H), 2.42 (s, 3 H),
2.26–2.11 (m, 1 H), 2.03 (td, J = 11.3, 3.3 Hz, 1 H), 1.73–1.44 (m, 4 H),
1.36–1.16 (m, 2 H), 1.07 (d, J = 6.2 Hz, 3 H).
13C NMR (75 MHz, CDCl3): = 143.9, 136.4, 131.8, 129.9, 128.8, 127.1,
118.0, 107.0, 55.9, 54.4, 52.0, 48.3, 34.7, 26.1, 24.1, 21.7, 19.2.
HRMS (EI): m/z [M]+ calcd for C19H28N2O2S: 348.1871; found:
348.1879.
IR (ATR): 2932, 2853, 2800, 2759, 1656, 1357, 1306, 1164, 1090,
665 cm–1
.
1H NMR (300 MHz, CDCl3): = 7.65 (d, J = 8.2 Hz, 2 H), 7.29 (d, J = 8.2
Hz, 2 H), 6.75 (dt, J = 14.2, 1.2 Hz, 1 H), 5.63 (ddt, J = 17.2, 10.5, 5.3 Hz,
1 H), 5.23–5.09 (m, 2 H), 4.85 (dt, J = 14.2, 7.2 Hz, 1 H), 3.99 (dt, J = 5.4,
1.7 Hz, 2 H), 2.93 (dd, J = 7.2, 1.2 Hz, 2 H), 2.42 (s, 3 H), 2.32 (br t,
J = 5.5 Hz, 4 H), 1.62–1.35 (m, 6 H).
13C NMR (75 MHz, CDCl3): = 143.9, 136.4, 131.7, 129.9, 128.8, 127.1,
118.0, 107.9, 59.7, 54.3, 48.3, 26.0, 24.5, 21.7.
Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–J