The Journal of Organic Chemistry
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57.69 (s, 3F), ꢀ62.87 (s, 3F). 13C NMR (101 MHz, CDCl3) δ 138.1 (q, J = 5.8 Hz), 137.2 (s), 130.9 (q, J = 32.7 Hz), 129.0 (q, J = 2.4 Hz),
125.3 (q, J = 3.7 Hz), 122.4 (q, J = 271.5 Hz), 121.2 (q, J = 272.2 Hz), 120.3 (q, J = 35.0 Hz). The spectral data are in accordance with
literature report.9a
(Z)-4-(3,3,3-trifluoroprop-1-en-1-yl)benzonitrile (4i; 7 mg, 36%). Colorless oil; 1H NMR (400 MHz, CDCl3) δ 7.69 (d, J = 8.3 Hz, 2H),
7.49 (d, J = 8.2 Hz, 2H), 6.98 (d, J = 12.6 Hz, 1H), 5.95 (dq, J = 12.6, 8.7 Hz, 1H). 19F NMR (376 MHz, CDCl3) δ ꢀ57.72 (s, 3F). 13C
NMR (101 MHz, CDCl3) δ 138.2 (s), 137.6 (q, J = 5.7 Hz), 132.1 (s), 129.3 (q, J = 2.5 Hz), 122.3 (q, J = 271.7 Hz), 121.0 (q, J = 35.0
Hz), 118.3 (s), 112.7 (s). The spectral data are in accordance with literature report.9a, 25
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(Z)-1-(4-(3,3,3-trifluoroprop-1-en-1-yl)phenyl)ethan-1-one (4j; 11 mg, 51%). Colorless oil; H NMR (400 MHz, CDCl3) δ 7.98 (d, J =
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8.4 Hz, 2H), 7.49 (d, J = 8.2 Hz, 2H), 7.00 (d, J = 12.6 Hz, 1H), 5.91 (dq, J = 12.6, 8.8 Hz, 1H), 2.64 (s, 3H). 19F NMR (376 MHz,
CDCl3) δ ꢀ57.64 (s, 3F). 13C NMR (101 MHz, CDCl3) δ 197.4 (s), 138.5 (q, J = 5.8 Hz), 138.3 (s), 137.1 (s), 129.0 (q, J = 2.5 Hz), 128.3
(s), 122.5 (q, J = 271.5 Hz), 120.0 (q, J = 35.0 Hz), 26.6 (s). The spectral data are in accordance with literature report.3f
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Methyl (Z)-4-(3,3,3-trifluoroprop-1-en-1-yl)benzoate (4k; 13 mg, 57%). Colorless oil; H NMR (400 MHz, CDCl3) δ 8.06 (d, J = 8.4
Hz, 2H), 7.47 (d, J = 8.2 Hz, 2H), 7.00 (d, J = 12.6 Hz, 1H), 5.90 (dq, J = 12.6, 8.8 Hz, 1H), 3.95 (s, 3H). 19F NMR (376 MHz, CDCl3) δ ꢀ
57.66 (s, 3F). 13C NMR (101 MHz, CDCl3) δ 166.6 (s), 138.6 (q, J = 5.8 Hz), 138.1 (s), 130.4 (s), 129.5 (s), 128.8 (q, J = 2.5 Hz), 122.5
(q, J = 271.5 Hz), 119.9 (q, J = 34.9 Hz), 52.2 (s). The spectral data are in accordance with literature report.23,25
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(Z)-3-(3,3,3-trifluoroprop-1-en-1-yl)aniline (4m; 8 mg; 43%). Yellow oil; H NMR (400 MHz, CDCl3) δ 7.19 (t, J = 7.8 Hz, 1H), 6.88
(d, J = 12.7 Hz, 1H), 6.83 (d, J = 7.7 Hz, 1H), 6.76 (m, 1H), 6.70 (dd, J = 7.9, 2.0 Hz, 1H), 5.75 (dq, J = 12.6, 9.1 Hz, 1H), 3.61 (s, 2H).
19F NMR (376 MHz, CDCl3) δ ꢀ57.30 (s, 3F). Anal. Calcd for C9H8F3N: C, 57.76; H, 4.31; N, 7.48. Found: C, 58.05; H, 4.11; N, 7.26.
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(Z)-1-methyl-3-(3,3,3-trifluoroprop-1-en-1-yl)benzene (4n; 8 mg; 43%). Colorless oil; H NMR (400 MHz, CDCl3) δ 7.41 – 7.17 (m,
4H), 6.93 (d, J = 12.6 Hz, 1H), 5.77 (dq, J = 12.6, 9.1 Hz, 1H), 2.39 (s, 3H). 19F NMR (376 MHz, CDCl3) δ ꢀ57.49 (s, 3F). 13C NMR (101
MHz, CDCl3) δ 139.8 (q, J = 5.9 Hz), 137.9 (s), 129.8 (s), 129.6 (q, J = 2.4 Hz), 128.2 (s), 126.0 (q, J = 2.6 Hz), 122.8 (q, J = 271.3 Hz),
117.8 (q, J = 34.9 Hz), 113.6 (s), 21.3 (s). The spectral data are in accordance with literature report.26
(Z)-1-chloro-2-(3,3,3-trifluoroprop-1-en-1-yl)benzene (4o; 5 mg, 22%). Yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.49 – 7.40 (m, 2H),
7.36 – 7.28 (m, 2H), 7.11 (d, J = 12.4 Hz, 1H), 5.93 (dq, J = 12.3, 8.5 Hz, 1H). 19F NMR (376 MHz, CDCl3) δ ꢀ57.93 (s, 3F). 13C NMR
(101 MHz, CDCl3) δ 136.6 (q, J = 5.7 Hz), 133.2 (s), 130.3 (q, J = 3.3 Hz), 130.1 (s), 129.2 (s), 126.6 (s), 122.6 (q, J = 271.7 Hz), 120.0
(q, J = 34.3 Hz), 116.5 (s). The spectral data are in accordance with literature report.9a
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(Z)-3-(3,3,3-trifluoroprop-1-en-1-yl)pyridine (4p; 4 mg, 23%). Yellow oil; H NMR (400 MHz, CDCl3) δ 9.03 (s, 2H), 7.83 (d, J = 7.7
Hz, 1H), 7.56 (d, J = 8.8 Hz, 1H), 6.97 (d, J = 12.6 Hz, 1H), 5.97 (dq, J = 12.6, 8.8 Hz, 1H). 19F NMR (376 MHz, CDCl3) δ ꢀ57.89 (s, 3F).
The spectral data are in accordance with literature report.24
Phenylꢀtrifluoromethylation product using Ph3SiH as the silane:
Yellow oil, 12 mg, 42% yield. 1H NMR (400 MHz, CDCl3) δ 7.38 (m, 5H), 7.27 (dd, J = 8.1, 1.4 Hz, 2H), 7.22 (d, J = 8.4 Hz, 2H), 6.17
(q, J = 8.2 Hz, 1H). 19F NMR (376 MHz, CDCl3) δ ꢀ55.57 (s). 13C NMR (101 MHz, CDCl3) δ 151.3 (q, J = 5.6 Hz), 139.7 (s), 135.7 (s),
134.7 (s), 130.5 (d, J = 1.8 Hz), 129.7 (s), 128.6 (s), 128.4 (s), 127.9 (s), 123.0 (q, J = 270.7 Hz), 116.0 (q, J = 34.0 Hz). The spectral data
are in accordance with literature report.7d
(E)-1-(1-(4-chlorophenyl)-3,3,3-trifluoroprop-1-enyl)-2,2,6,6-tetramethylpiperidine (6; 9 mg, 26%). Colorless oil; 1H NMR (400
MHz, CDCl3) δ 7.67 – 7.30 (m, 4H), 6.01 (q, J = 8.7 Hz, 1H), 1.87 – 1.48 (m, 6H), 1.19 (s, 12H). 19F NMR (376 MHz, CDCl3) δ ꢀ51.80
(s, 3F). 13C NMR (101 MHz, CDCl3) δ 165.6 (q, J = 5.6 Hz), 135.8 (s), 131.7 (s), 129.7 (q, J = 1.7 Hz), 128.4 (s), 125.6 (q, J = 266.5 Hz),
94.8 (q, J = 35.6 Hz), 61.0 (s), 39.6 (s), 32.1 (s), 20.7 (s), 16.9 (s). Anal. Calcd for C18H23ClF3N: C, 62.51; H, 6.70; N, 4.05. Found: C,
62.77; H, 6.59; N, 4.11.
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