The Journal of Organic Chemistry
Article
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-(1-Methoxy-10H-phenothiazin-10-yl)ethan-1-one (4c). Com-
127.4, 23.1. HRMS(ESI) m/z: [M + H] calcd for C H ClNOS
14 11
pound 4c was prepared from 1c and 2a following the general
procedure. Purification by column chromatography on silica gel
276.0244; Found 276.0248.
1-(2-Nitro-10H-phenothiazin-10-yl)ethan-1-one (4i). Compound
4i was prepared from 1i and 2a following the general procedure.
Purification by column chromatography on silica gel (PET/EA = 8:1)
yielded 4i (113 mg, 33%) as a yellow solid. mp: 157.3−159.1 °C. H
NMR (500 MHz, DMSO-d ): δ 8.44 (s, 1H), 8.15 (dd, J = 8.6, 1.9
(
PET/EA = 8:1) yielded 4c (114 mg, 35%) as a white solid. mp:
1
1
64.7−166.3 °C. H NMR (500 MHz, DMSO-d ): δ 7.54 (d, J = 4.0
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1
Hz, 2H), 7.38−7.31 (m, 2H), 7.28 (d, J = 7.4 Hz, 1H), 7.18 (d, J =
7
.7 Hz, 1H), 7.14 (d, J = 8.2 Hz, 1H), 3.92 (s, 3H), 1.99 (s, 3H).
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13
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C{ H} NMR (126 MHz, DMSO-d ): δ 169.4, 154.3, 139.2, 135.3,
Hz, 1H), 7.82 (d, J = 8.7 Hz, 1H), 7.70 (d, J = 7.9 Hz, 1H), 7.61 (d, J
= 7.7 Hz, 1H), 7.47 (t, J = 7.6 Hz, 1H), 7.37 (t, J = 7.5 Hz, 1H), 2.19
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1
32.2, 128.9, 128.5, 127.9, 127. 8, 127.3, 127.1, 120.6, 111.9, 56.5,
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21.6. HRMS(ESI) m/z: [M + H] calcd for C H NO S 272.0745;
(s, 3H). C{ H} NMR (126 MHz, DMSO-d
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): δ 169.0, 146.7, 141.3,
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Found 272.0748.
139.0, 138.1, 130.9, 128.9, 128.6, 128.5, 128.1, 127.9, 122.7, 122.1,
23.0. HRMS(ESI) m/z: [M + H] calcd for C14H N O S 287.0490;
11 2 3
Found 287.0485.
1-(2-(Trifluoromethyl)-10H-phenothiazin-10-yl)ethan-1-one (4j).
Compound 4j was prepared from 1j and 2a following the general
procedure. Meanwhile, 4j was also prepared from 1a and 2d following
the general procedure 4. Purification by column chromatography on
silica gel (PET/EA = 8:1) yielded 4j (159 mg, 43% or 186 mg, 50%)
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1
-(2-Methyl-10H-phenothiazin-10-yl)ethan-1-one (4e). Com-
pound 4e was prepared from 1e and 2a following the general
procedure. Meanwhile, 4e was also prepared from 1a and 2b following
the general procedure 4. Purification by column chromatography on
silica gel (PET/EA = 8:1) yielded 4e (207 mg, 68% or 229 mg, 75%)
1
as a yellow solid. mp: 198.9−200.1 °C. H NMR (500 MHz, DMSO-
d ): δ 7.61 (d, J = 7.9 Hz, 1H), 7.54 (d, J = 7.7 Hz, 1H), 7.46 (s, 1H),
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1
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1
.42 (d, J = 8.0 Hz, 1H), 7.38 (t, J = 7.7, 1H), 7.29(t, J = 7.6, 1.2 Hz,
H), 7.12 (d, J = 7.9 Hz, 1H), 2.33 (s, 3H), 2.12 (s, 3H). C{ H}
as a white solid. mp: 224.3−226.1 °C. H NMR (500 MHz, DMSO-
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d ): δ 7.99 (s, 1H), 7.80 (d, J = 8.2 Hz, 1H), 7.70−7.65 (m, 2H), 7.60
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NMR (126 MHz, DMSO-d ): δ 168.9, 139.2, 139.1, 137.5, 132.8,
(dd, J = 7.8, 1.3 Hz, 1H), 7.45−7.43 (m, 1H), 7.36−7.34 (m, 1H),
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29.0, 128.3, 128.2, 128.1, 128.0, 127.9, 127.6, 127.3, 23.2, 21.0.
2.16 (s, 3H). C{ H} NMR (126 MHz, DMSO-d
): δ 168.9, 139.2,
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HRMS(ESI) m/z: [M + H] calcd for C H NOS 256.0796; Found
138.5, 137.8, 131.5, 129.2, 128.5, 128.3, 127.9, 124.70, 124.67,
124.3(q, JC‑F = 270.6 Hz), 123.93, 123.90, 23.0. F NMR (471 MHz,
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56.0800.
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-(2-Methoxy-10H-phenothiazin-10-yl)ethan-1-one (4f). Com-
DMSO-d ): δ −60.85. HRMS(ESI) m/z: [M + H] calcd for
6
pound 4f was prepared from 1f and 2a following the general
procedure. Purification by column chromatography on silica gel
C H F NOS 310.0513; Found 310.0516.
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1-(3-Methyl-10H-phenothiazin-10-yl)ethan-1-one (4k). Com-
(
PET/EA = 8:1) yielded 4f (276 mg, 85%) as a white solid. mp:
pound 4k was prepared from 1k and 2a following the general
procedure. Purification by column chromatography on silica gel
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80.1−182.2 °C. H NMR (500 MHz, DMSO-d ): δ 7.60 (d, J = 7.9
6
Hz, 1H), 7.53 (d, J = 7.6 Hz, 1H), 7.44 (d, J = 8.7 Hz, 1H), 7.38 (t, J
(PET/EA = 8:1) yielded 4k (564 mg, 92%) as a white solid. mp:
1
=
7.7 Hz, 1H), 7.30−7.27 (m, 2H), 6.92 (dd, J = 8.7, 2.6 Hz, 1H),
208.8−210.1 °C. H NMR (500 MHz, DMSO-d ): δ 7.60 (d, J = 7.9
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3
1
3
1
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.78 (s, 3H), 2.15 (s, 3H). C{ H} NMR (126 MHz, DMSO-d ): δ
Hz, 1H), 7.53 (d, J = 7.7 Hz, 1H), 7.49 (d, J = 8.1 Hz, 1H), 7.40−
7.35 (m, 2H), 7.29 (t, J = 7.5 Hz, 1H), 7.19 (d, J = 8.1 Hz, 1H), 2.31
(s, 3H), 2.11 (s, 3H). C{ H} NMR (126 MHz, DMSO-d ): δ 169.0,
6
68.9, 159.3, 140.5, 139.2, 133.1, 128.8, 128.2, 127.9, 127.5, 127.3,
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23.2, 113.8, 113.7, 56.1, 23.3. HRMS(ESI) m/z: [M + H] calcd for
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C H NO S 272.0745; Found 272.0750.
139.2, 137.1, 136.6, 132.4, 132.2, 128.4, 128.2, 127.9, 127.6, 127.459,
127.451, 127.3, 23.1, 20.8. HRMS(ESI) m/z: [M + H] calcd for
15
14
2
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1
-(2-Fluoro-10H-phenothiazin-10-yl)ethan-1-one (4g). Com-
pound 4g was prepared from 1g and 2a following the general
procedure. Meanwhile, 4g was also prepared from 1a and 2e following
the general procedure 4. Purification by column chromatography on
silica gel (PET/EA = 8:1) yielded 4g (96 mg, 31% or 115 mg, 37%)
C H NOS 256.0791; Found 256.0798.
1-(3-Methoxy-10H-phenothiazin-10-yl)ethan-1-one (4l). Com-
pound 4l was prepared from 1l and 2a following the general
procedure. Meanwhile, 4l was prepared from 1a and 2d following the
general procedure 4. Purification by column chromatography on silica
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as a yellow solid. mp:216.3−217.6 °C. H NMR (500 MHz, DMSO-
d ): δ 7.62 (d, J = 7.9 Hz, 1H), 7.60−7.54 (m, 3H), 7.41 (t, J = 7.6
gel (PET/EA = 8:1) yielded 4l (289 mg, 89% or 179 mg, 55%) as a
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Hz, 1H), 7.32 (d, J = 15.0 Hz, 1H), 7.21−7.18 (m, 1H), 2.16 (s, 3H).
white solid. mp: 214.8−217.2 °C. H NMR (500 MHz, DMSO-d ): δ
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C{ H} NMR (126 MHz, DMSO-d ): δ 168.9, 161.5(d, J = 242.6
7.60 (d, J = 7.7 Hz, 1H), 7.53 (t, J = 9.2 Hz, 2H), 7.39 (t, J = 7.5 Hz,
1H), 7.30 (t, J = 7.5 Hz, 1H), 7.13 (d, J = 2.2 Hz, 1H), 6.95 (dd, J =
6
C‑F
Hz), 140.6, 138.7, 129.43, 129.35, 128.4, 127.9, 127.6, 115.5, 115.3,
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14.9, 114.7, 23.2. F NMR (471 MHz, DMSO-d ): δ −114.74.
8.8, 2.6 Hz, 1H), 3.78 (s, 3H), 2.10 (s, 3H). C{ H} NMR (126
MHz, DMSO-d ): δ 169.1, 158.0, 139.5, 131.9, 128.51, 128.49, 128.2,
127.9, 127.7, 127.3, 113.90, 113.88, 112.7, 56.1, 23.1. HRMS(ESI) m/
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HRMS(ESI) m/z: [M + H] calcd for C H FNOS 260.0540; Found
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1
4
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60.0543.
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-(4-Fluoro-10H-phenothiazin-10-yl)ethan-1-one (4g-1). Com-
z: [M + H] calcd for C15H14NO S 272.0740; Found 272.0745.
2
pound 4g-1 was prepared from 1g and 2a following the general
procedure. Purification by column chromatography on silica gel
1-(3-Ethoxy-10H-phenothiazin-10-yl)ethan-1-one (4m). Com-
pound 4m was prepared from 1m and 2a following the general
procedure. Purification by column chromatography on silica gel
(
PET/EA = 8:1) yielded 4g-1 (65 mg, 21%) as a white solid. mp:
1
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79.8−181.5 °C. H NMR (500 MHz, DMSO-d ): δ 7.65 (d, J = 7.9
(PET/EA = 8:1) yielded 4m (226 mg, 69%) as a white solid. mp:
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Hz, 1H), 7.62(d, J = 7.8 Hz, 1H), 7.51 (d, J = 7.9 Hz, 1H), 7.48−
204.5−206.8 °C. H NMR (500 MHz, DMSO-d
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): δ 7.60 (d, J = 7.6
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.42(m, 2H), 7.34 (t, J = 7.5 Hz, 1H), 7.29 (t, J = 8.6 Hz, 1H), 2.15
Hz, 1H), 7.54 (dd, J = 7.7, 0.9 Hz, 1H), 7.51 (d, J = 8.6 Hz, 1H),
7.38−7.36 (m, 1H), 7.29 (t, J = 7.4 Hz, 1H), 7.10 (d, J = 2.6 Hz, 1H),
6.93 (dd, J = 8.8, 2.8 Hz, 1H), 4.04 (dd, J = 6.9, 2.6 Hz, 2H), 2.10 (s,
1
(
s, 3H). 13C{ H} NMR (126 MHz, DMSO-d ): δ 169.0, 158.6(d, J
6 C‑F
=
242.2 Hz), 141.0, 139.0, 128.8, 128.7, 128.6, 128.2, 128.1, 127.7,
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24.0, 114.0, 113.8, 23.2. F NMR (471 MHz, DMSO): δ −113.17.
3H), 1.32 (t, J = 7.0 Hz, 3H). C{ H} NMR (126 MHz, DMSO-d ):
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HRMS(ESI) m/z: [M + H] calcd for C H FNOS 260.0540; Found
δ 169.1, 157.3, 139.5, 131.8, 128.5, 128.2, 127.9, 127.8, 127.61,
127.58, 127.2, 114.3, 113.1, 64.1, 23.1, 15.0. HRMS(ESI) m/z: [M +
1
4
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60.0546.
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-(2-Chloro-10H-phenothiazin-10-yl)ethan-1-one (4h). Com-
H] calcd for C H NO S 286.0896; Found 286.0904.
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pound 4h was prepared from 1h and 2a following the general
procedure. Purification by column chromatography on silica gel
1-(3-Chloro-10H-phenothiazin-10-yl)ethan-1-one (4n). Com-
pound 4n was prepared from 1n and 2a following the general
procedure. Purification by column chromatography on silica gel
(
PET/EA = 8:1) yielded 4h (172 mg, 52%) as a yellow solid. mp:
1
1
7
1
2
1
98.7−200.4 °C. H NMR (500 MHz, DMSO-d ): δ 7.73(s, 1H),
(PET/EA = 8:1) yielded 4n (156 mg, 47%) as a white solid. mp:
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.63 (d, J = 7.9 Hz, 1H), 7.58−7.54 (m, 2H), 7.42 (td, J = 7.8, 1.3 Hz,
H), 7.37 (dd, J = 8.4, 2.2 Hz, 1H), 7.32 (td, J = 7.7, 1.1 Hz, 1H),
204.5−206.8 °C. H NMR (500 MHz, DMSO-d ): δ 7.70 (d, J = 2.1
6
Hz, 1H), 7.66−7.61 (m, 2H), 7.57 (d, J = 7.7 Hz, 1H), 7.47−7.40 (m,
2H), 7.33 (t, J = 7.6 Hz, 1H), 2.13 (s, 3H). C{ H} NMR (126
.14 (s, 3H). 13C{ H} NMR (126 MHz, DMSO-d ): δ 168.9, 140.2,
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13
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38.7, 132.1, 132.0, 131.5, 129.4, 128.4, 128.0, 127.9, 127.8, 127.7,
MHz, DMSO-d ): δ 168.9, 138.9, 137.9, 134.7, 131.7, 131.5, 130.3,
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628
J. Org. Chem. 2021, 86, 6622−6632