The Journal of Organic Chemistry
Article
2
13C{1H} NMR (101 MHz, CDCl3): δ 143.7, 140.2, 133.2 (t, JC‑F
=
(2r) Purified by flash column chromatography (petroleum ether),
white solid (16 mg, 90% yield); mp: 68−70 °C. 1H NMR (400 MHz,
CDCl3): δ 7.99 (s, 0.83H), 7.96−7.88 (m, 3H), 7.62 (d, J = 8.2 Hz,
1H), 7.60−7.54 (m, 1.84H). 19F{1H} NMR (375 MHz, CDCl3): δ
−110.5 (t, J = 8.7 Hz), 6.82 (t, J = 56.4 Hz, 0.03H). 13C{1H} NMR
(101 MHz, CDCl3): δ 134.3, 132.6, 131.6 (t, 2JC‑F = 22.3 Hz), 128.9,
3
22.5 Hz), 128.9, 127.9, 127.5, 127.3,126.1 (t, JC‑F = 5.9 Hz), 114.4
(tt, 1JC‑F = 238.4 Hz, JC−D = 28.7 Hz). HRMS (ESI) m/z: [M + H]+
calcd for C13H10DF2 206.0886; found 206.0881.
(2k) Purified by flash column chromatography (petroleum ether/
ethyl acetate = 40:1), Pale-yellow solid (13 mg, 70% yield); mp: 41−
42 °C. 1H NMR (600 MHz, CDCl3): δ 8.12 (d, J = 8.0 Hz, 2H), 7.59
(d, J = 8.0 Hz, 2H), 6.69 (t, J = 56.1 Hz, 0.16H), 3.94 (s, 3H).
19F{1H} NMR (565 MHz, CDCl3): δ −113.0 (t, J = 8.8 Hz). 13C{1H}
NMR (150 MHz, CDCl3): δ 166.2, 138.4 (t, 2JC‑F = 22.5 Hz), 132.3,
3
3
128.5, 127.9, 127.4, 126.8, 125.9 (t, JC‑F = 7.5 Hz), 122.0 (t, JC‑F
=
1
4.5 Hz), 114.7 (tt, JC‑F = 237.6 Hz, JC−D = 28.4 Hz). HRMS (ESI)
m/z: [M − F]+ calcd for C11H7DF 160.0667; found 160.0667.
(2s) Purified by flash column chromatography (petroleum ether),
yellow solid (19 mg, 83% yield); mp: 59−60 °C. 1H NMR (600 MHz,
CDCl3): δ 8.57 (s, 1H), 8.47 (d, J = 8.9 Hz, 2H), 8.04 (d, J = 8.5 Hz,
2H), 8.02 (t, J = 53.7 Hz, 0.64H), 7.61 (t, J = 7.3 Hz, 2H), 7.52 (t, J =
7.7 Hz, 2H). 19F{1H} NMR (565 MHz, CDCl3): δ -107.3 (t, J = 8.2
3
1
129.9, 125.6 (t, JC‑F = 6.0 Hz), 113.7 (tt, JC‑F = 238.7 Hz, JC−D
=
28.4 Hz), 52.4. HRMS (ESI) m/z: [M − F]+ calcd for C9H7DFO2
168.0566; found 168.0563.
(2l) Purified by flash column chromatography (petroleum ether),
Hz). 13C{1H} NMR (150 MHz, CDCl3): δ 131.5, 131.1, 129.6 (t,
1
pale-yellow oil (13 mg, 78% yield). H NMR (400 MHz, CDCl3): δ
1
2JC‑F = 3.6 Hz), 129.2, 127.3, 125.2, 123.3, 123.2, 113.7 (tt, JC‑F
=
7.77 (d, J = 8.4 Hz, 2H), 7.63 (d, J = 8.5 Hz, 2H). 19F{1H} NMR
(375 MHz, CDCl3): δ −113.8 (t, J = 8.6 Hz). 13C{1H} NMR (101
MHz, CDCl3): δ 138.4 (t, 2JC‑F = 22.9 Hz), 132.6, 126.4 (t, 3JC‑F = 6.0
221.0 Hz, JC−D = 27.9 Hz). HRMS (ESI) m/z: [M − F]+ calcd for
C15H9DF 210.0824; found 210.0823.
1
Hz), 117.8, 114.8, 113.0 (tt, JC‑F = 240.7 Hz, JC−D = 28.8 Hz).
(2t) Not isolated due to high volatility, and in situ NMR data were
HRMS (ESI) m/z: [M + H]+ calcd for C8H5DF2N 155.0526; found
155.0525.
1
given. H NMR (600 MHz, DMSO-d6): δ 8.69 (d, J = 4.4 Hz, 1H),
8.00 (t, J = 7.3 Hz, 1H), 7.70 (d, J = 7.8 Hz, 1H), 7.58 (dd, J = 6.7,
5.3 Hz, 1H), 6.95 (t, J = 55.0 Hz, 0.08H). 19F{1H} NMR (565 MHz,
DMSO-d6): δ -116.0 (t, J = 8.7 Hz). 13C{1H} NMR (150 MHz,
(2m) Purified by flash column chromatography (petroleum ether),
colorless oil (12 mg, 76% yield). 1H NMR (600 MHz, CDCl3): δ 7.37
(d, J = 7.4 Hz, 1H), 7.09 (d, J = 7.5 Hz, 1H), 7.02 (d, J = 8.3 Hz,
0.05H), 3.84 (s, 3H). 19F{1H} NMR (565 MHz, CDCl3): δ -113.4 (t,
J = 8.6 Hz). 13C{1H} NMR (150 MHz, CDCl3): δ 159.7, 135.6 (t,
2JC‑F = 22.3 Hz), 129.7, 117.8 (t, 3JC‑F = 6.1 Hz), 116.3 (t, JC−D = 24.2
Hz), 114.3 (tt, 1JC‑F =237.9 Hz, JC−D = 28.5 Hz), 110.4 (tt, JC−D =24.0
2
DMSO-d6): δ 151.8 (t, JC‑F = 24.7 Hz), 149.6, 137.9, 126.0, 120.45
3
1
(t, JC‑F = 3.5 Hz), 113.5 (tt, JC‑F = 237.0 Hz, JC−D = 29.4 Hz).
HRMS (ESI) m/z: [M + H]+ calcd for C6H6F2D 131.0526; found
131.0531.
(2u) Purified by flash column chromatography (petroleum ether/
ethyl acetate = 80:1), white solid (15 mg, 84% yield); mp: 48−51 °C.
1H NMR (600 MHz, CDCl3): δ 8.31 (d, J = 8.5 Hz, 1H), 8.14 (d, J =
8.5 Hz, 1H), 7.87 (d, J = 8.1 Hz, 1H), 7.78 (t, J = 7.1 Hz, 1H), 7.73
(d, J = 8.5 Hz, 1H), 7.63 (t, J = 7.5 Hz, 1H). 19F{1H} NMR (565
MHz, CDCl3): δ -114.9 (t, J = 8.4 Hz). 13C{1H} NMR (150 MHz,
Hz, JC‑F = 5.9 Hz), 55.4. HRMS (ESI) m/z: [M + H]+ calcd for
3
C8H6D3F2O 162.0804; found 162.0798.
(2n) Purified by flash column chromatography (petroleum ether),
colorless oil (18 mg, 88% yield). 1H NMR (600 MHz, CDCl3): δ 7.75
(s, 1H), 7.72 (d, J = 7.5 Hz, 1H), 7.62 (d, J = 7.6 Hz, 2H), 7.55 (t, J =
7.6 Hz, 1H), 7.52−7.46 (m, 3H), 7.40 (t, J = 7.4 Hz, 1H), 6.73 (t, J =
56.5 Hz, 0.04H). 19F{1H} NMR (565 MHz, CDCl3): δ -111.3 (t, J =
8.7 Hz). 13C{1H} NMR (150 MHz, CDCl3): δ 141.9, 140.2, 134.9 (t,
2JC‑F = 22.2 Hz), 129.5, 129.2, 128.9, 127.8, 127.2, 124.4 (t, 3JC‑F = 5.7
Hz), 124.3 (t, 3JC‑F = 5.7 Hz), 114.6 (tt, 1JC‑F = 237.9 Hz, JC−D = 28.3
Hz). HRMS (ESI) m/z: [M + H]+ calcd for C13H10DF2 206.0886;
found 206.0889.
2
CDCl3): δ 152.7 (t, JC‑F = 26.8 Hz), 147.2, 137.8, 130.3, 129.7,
1
128.7, 127.9, 127.7, 116.8, 114.3 (tt, JC‑F = 239.6 Hz, JC−D = 29.0
Hz). HRMS (ESI) m/z: [M + H]+ calcd for C10H7DF2N 181.0682;
found 181.0680.
(2v) Purified by flash column chromatography (petroleum ether/
ethyl acetate = 100:1), white solid (16 mg, 87% yield); mp: 44−46
°C. 1H NMR (600 MHz, CDCl3): δ 7.89 (d, J = 8.9 Hz, 1H), 7.84 (d,
J = 8.9 Hz, 1H), 7.47−7.40 (m, 2H), 6.94 (t, J = 55.8 Hz, 0.03H).
19F{1H} NMR (565 MHz, CDCl3): δ -104.7 (t, J = 8.6 Hz). 13C{1H}
NMR (150 MHz, CDCl3): δ 140.2, 138.3, 136.3 (t, 2JC‑F = 25.7 Hz),
125.9, 126.1, 124.9, 124.7, 124.3 (tt, JC−D = 25.8 Hz, 3JC‑F = 7.3 Hz),
111.6 (tt, 1JC‑F = 236.5 Hz, JC−D = 28.8 Hz). HRMS (ESI) m/z: [M +
H]+ calcd for C9H5D2F2S 187.0357; found 187.0366.
(2o) Purified by flash column chromatography (petroleum ether),
colorless oil (10 mg, 53% yield). 1H NMR (600 MHz, CDCl3): δ 7.58
(d, J = 7.6 Hz, 1H), 7.43 (d, J = 7.3 Hz, 1H), 7.04 (t, J = 7.5 Hz, 1H),
6.97 (t, J = 55.6 Hz, 0.10H), 6.94 (d, J = 8.6 Hz, 0.11H), 3.87 (s, 3H).
19F{1H} NMR (565 MHz, CDCl3): δ −116.0 (t, J = 8.7 Hz). 13C{1H}
NMR (150 MHz, CDCl3): δ 157.2 (t, 3JC‑F = 5.9 Hz), 131.8, 126.2 (t,
3JC‑F = 5.8 Hz), 122.6 (t, JC‑F = 22.2 Hz), 120.6, 111.3 (tt, JC‑F
=234.4 Hz, JC−D = 24.4 Hz), 110.6 (t, JC−D = 24.4 Hz), 55.6. HRMS
(ESI) m/z: [M − F]+ calcd for C8H6D2FO 141.0679; found
141.0678.
2
1
(2w) Purified by flash column chromatography (petroleum ether/
1
ethyl acetate = 100:1), colorless oil (14 mg, 83% yield). H NMR
(600 MHz, CDCl3): δ 7.65 (d, J = 7.8 Hz, 1H), 7.55 (d, J = 8.3 Hz,
1H), 7.40 (t, J = 7.7 Hz, 1H), 7.30 (t, J = 7.5 Hz, 1H), 6.76 (t, J =
55.8 Hz, 0.04H). 19F{1H} NMR (565 MHz, CDCl3): δ -117.2 (t, J =
(2p) Purified by flash column chromatography (petroleum ether/
ethyl acetate = 8:1), beige solid (17 mg, 90% yield); mp: 60−62 °C.
1H NMR (400 MHz, CDCl3): δ 7.04 (s, J = 8.4 Hz, 0.87H), 3.91 (s,
3H), 3.90 (s, 3H). 19F{1H} NMR (375 MHz, CDCl3): δ -108.9 (t, J =
8.6 Hz). 13C{1H} NMR (101 MHz, CDCl3): δ 150.8, 149.2, 126.7 (t,
2JC‑F = 22.7 Hz), 118.6 (t, 3JC‑F = 6.9 Hz), 114.6 (tt, 1JC‑F = 237.5 Hz,
8.3 Hz). 13C{1H} NMR (150 MHz, CDCl3): δ 155.2, 148.3 (t, 2JC‑F
=
1
29.1 Hz), 126.6, 126.1, 123.6, 122.1, 111.9, 108.4 (tt, JC‑F = 235.0
3
Hz, JC−D = 28.6 Hz), 106.7 (tt, JC−D = 27.2 Hz, JC‑F = 4.5 Hz).
HRMS (ESI) m/z: [M − F]+ calcd for C9H4D2FO 151.0523; found
151.0520.
J
C−D = 28.6 Hz), 110.4 (t, JC−D = 22.8 Hz), 107.8 (tt, JC−D = 24.9 Hz,
(2x) Purified by flash column chromatography (petroleum ether/
ethyl acetate = 5:1), white solid (15 mg, 82% yield); mp: 65−66 °C.
1H NMR (600 MHz, CDCl3): δ 7.82 (d, J = 8.1 Hz, 1H), 7.43−7.40
(m, 2H), 7.34 (t, J = 7.5 Hz, 1H), 4.00−3.90 (m, 1.72H). 19F{1H}
NMR (565 MHz, CDCl3): δ −114.5 (t, J = 7.8 Hz). 13C{1H} NMR
(150 MHz, CDCl3): δ 144.8 (t, 2JC‑F = 27.4 Hz), 141.7, 136.3, 124.8,
123.1, 121.0, 111.0 (tt, Hz, 1JC‑F = 206.6 Hz, JC−D = 29.4 Hz), 109.9,
30.5 (m). HRMS (ESI) m/z: [M + H]+ calcd for C9H5D4F2N2
187.0979; found 187.0975.
3JC‑F = 5.3 Hz), 56.1, 56.0. HRMS (ESI) m/z: [M + Na]+ calcd for
C9H7D3F2NaO2 214.0729; found 214.0724.
(2q) Purified by flash column chromatography (petroleum ether),
colorless oil (17 mg, 90% yield). 1H NMR (600 MHz, CDCl3): δ 8.19
(d, J = 8.4 Hz, 1H), 7.97 (d, J = 8.2 Hz, 1H), 7.93 (d, J = 8.1 Hz, 1H),
7.71 (d, J = 7.0 Hz, 1H), 7.61 (t, J = 7.1 Hz, 1H), 7.57 (t, J = 7.4 Hz,
1H), 7.51 (t, J = 7.7 Hz, 1H), 7.15 (t, J = 55.2 Hz, 0.04H). 19F{1H}
NMR (565 MHz, CDCl3): δ -111.6 (t, J = 8.4 Hz). 13C{1H} NMR
(150 MHz, CDCl3): δ 133.8, 131.5, 129.8, 129.5 (t, 2JC‑F = 20.8 Hz),
(2y) Purified by flash column chromatography (petroleum ether),
3
1
128.8, 127.2, 126.4, 124.8 (t, JC‑F = 8.6 Hz), 124.7, 123.6, 115.1 (tt,
colorless oil (12 mg, 71% yield). H NMR (600 MHz, CDCl3): δ
1JC‑F = 237.4 Hz, JC−D = 28.2 Hz). HRMS (ESI) m/z: [M − F]+ calcd
7.42−7.37 (m, 2H), 7.35−7.30 (m, 3H), 6.71 (s, 0.02H), 6.11 (t, J =
for C11H7DF 160.0667; found 160.0668.
56.3 Hz, 0.04H), 2.06 (s, 0.06H). 19F{1H} NMR (565 MHz, CDCl3):
3986
J. Org. Chem. 2021, 86, 3981−3988