The Journal of Organic Chemistry
Article
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Hz, 1H), 7.19 (t, J = 7.3 Hz, 1H), 2.27 (s, 3H) ppm; 13C{1H} NMR
(100 MHz, CDCl3): δ 186.6, 186.5, 138.1, 137.0, 136.8, 133.3, 132.4,
128.9, 128.2, 128.1 (×2), 125.4, 84.5, 21.1 ppm; HRMS-EI m/z:
[M]+ calcd for C16H12N2O2, 264.0899; found, 264.0900.
711 cm−1; H NMR (400 MHz, CDCl3): δ 7.57 (br d, J = 7.8 Hz,
2H), 7.51−7.44 (m, 3H), 7.37−7.31 (m, 2H), 7.27 (br d, J = 8.5 Hz,
2H) ppm; 13C{1H} NMR (100 MHz, CDCl3): δ 185.8, 185.4, 138.8,
136.7, 135.2, 132.8, 129.8, 128.5, 128.4, 128.2, 84.5 ppm; HRMS-EI
m/z: [M]+ calcd for C15H9ClN2O2, 284.0353; found, 284.0351.
2-Diazo-1-(4-methoxyphenyl)-3-phenylpropane-1,3-dione (1l).
The titled compound was prepared from 5l (0.545 g, 2.14 mmol)
by following the general procedure. Purification by chromatography
(hexane/EtOAc = 40:1, 5:1) provided 1l as yellow oil (0.535 g, 89%).
IR (neat): 3060, 2935, 2108, 1639, 1600, 1574, 1257, 1172, 902, 862,
1-(3-Chlorophenyl)-2-diazo-3-phenylpropane-1,3-dione (1f).
The titled compound was prepared from 5f (0.353 g, 1.37 mmol)
by following the general procedure. Purification by chromatography
(hexane/EtOAc = 30:1, 5:1) provided 1f as yellow oil (0.39 g,
quant.). IR (neat): 3064, 2115, 1652, 1646, 1636, 1598, 1296, 911,
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869, 732 cm−1; H NMR (400 MHz, CDCl3): δ 7.55 (br d, J = 7.8
791, 715 cm−1; H NMR (400 MHz, CDCl3): δ 7.58 (br d, J = 8.9
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Hz, 2H), 7.50 (t, J = 1.8 Hz, 1H), 7.48−7.35 (m, 3H), 7.32 (br t, J =
7.9 Hz, 2H), 7.22 (t, J = 7.9 Hz, 1H) ppm; 13C{1H} NMR (100 MHz,
CDCl3): δ 185.8, 185.3, 138.4, 136.7, 134.4, 132.8, 132.3, 129.5,
128.4 (×2), 128.2, 126.4, 85.0 ppm; HRMS-EI m/z: [M]+ calcd for
C15H9ClN2O2, 284.0353; found, 284.0360.
Hz, 4H), 7.45 (br t, J = 7.4 Hz, 1H), 7.33 (br t, J = 7.8 Hz, 2H), 6.80
(d, J = 8.8 Hz, 2H), 3.80 (s, 3H) ppm; 13C{1H} NMR (100 MHz,
CDCl3): δ 186.6, 184.9, 163.2, 137.0, 132.5, 130.8, 129.3, 128.3,
128.2, 113.5, 83.5, 55.4 ppm; HRMS-EI m/z: [M]+ calcd for
C16H12N2O3, 280.0848; found, 280.0841.
2-Diazo-1-phenyl-3-[4-(trifluoromethyl)phenyl]propane-1,3-
dione (lm). The titled compound was prepared from 5m (0.59 g, 2.02
mmol) by following the general procedure. Purification by
chromatography (hexane/EtOAc = 40:1, 5:1) provided 1m as yellow
oil (0.612 g, 95%). IR (neat): 3279, 3064, 2153, 1650, 1600, 1320,
1287, 1129, 858, 720, 700 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.64
(d, J = 8.4 Hz, 2H), 7.57 (br d, J = 8.3 Hz, 4H), 7.47 (br t, J = 7.4 Hz,
1H), 7.34 (t, J = 7.8 Hz, 2H), ppm; 13C{1H} NMR (100 MHz,
CDCl3): δ 185.9, 185.4, 140.1, 136.6, 133.6 (q, JC−F = 32.5 Hz),
2-Diazo-1-(3-methoxyphenyl)-3-phenylpropane-1,3-dione (1g).
The titled compound was prepared from 5g (0.54 g, 2.12 mmol)
by following the general procedure. Purification by chromatography
(hexane/EtOAc = 20:1, 5:1) provided 1g as yellow oil (0.60 g,
quant.). IR (neat): 3063, 2941, 2117, 1652, 1646, 1636, 1597, 1289,
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917, 792, 740 cm−1; H NMR (400 MHz, CDCl3): δ 7.56 (br d, J =
7.0 Hz, 2H), 7.43 (tt, J = 7.4, 1.3 Hz, 1H), 7,31 (br t, J = 7.9 Hz, 2H),
7.21 (t, J = 7.9 Hz, 1H), 7.14 (dt, J = 7.6, 1.3 Hz, 1H), 7.08 (dd, J =
2.4, 1.8 Hz, 1H), 6.97 (ddd, J = 8.1, 2.6, 1.0 Hz, 1H), 3.75 (s, 3H)
ppm; 13C{1H} NMR (100 MHz, CDCl3): δ 186.5, 186.0, 159.4,
138.1, 136.9, 132.5, 129.3, 128.3, 128.2, 120.7, 119.0, 112.8, 84.4, 55.3
ppm; HRMS-EI m/z: [M]+ calcd for C16H12N2O3, 280.0848; found,
280.0839.
132.9, 128.6, 128.5, 128.2, 125.2 (q, JC−F = 3.7 Hz), 123.4 (q, JC−F
=
270.9 Hz), 85.1 ppm; HRMS-EI m/z: [M]+ calcd for C16H9F3N2O2,
318.0616; found, 318.0612.
1-(Benzo[d][1,3]dioxol-5-yl)-2-diazo-3-phenylpropane-1,3-dione
(1n). The titled compound was prepared from 5n (0.42 g, 1.57 mmol)
by following the general procedure. Purification by chromatography
(hexane/EtOAc = 20:1, 5:1) provided 1n as yellow oil (0.46 g,
quant.). IR (neat): 3060, 2904, 2118, 1644, 1630, 1289, 1258, 931,
2-Diazo-1-(3-nitrophenyl)-3-phenylpropane-1,3-dione (1h). The
titled compound was prepared from 5h (0.307 g, 1.14 mmol) by
following the general procedure [Note: due to the poorer solubility,
more CH3CN (33 mL) was used to dissolve 5h than the typically
required amount (23 mL)]. Purification by chromatography (hexane/
EtOAc = 20:1, 3:1) provided 1h as yellow oil (0.339 g, quant.). IR
(neat): 3085, 2122, 1652, 1646, 1636, 1578, 1306, 917, 843, 718
cm−1; 1H NMR (400 MHz, CDCl3): δ 8.31 (t, J = 1.9 Hz, 1H), 8.23
(ddd, J = 8.2, 2.1, 1.0 Hz, 1H), 7.84 (dt, J = 7.8, 1.2 Hz, 1H), 7.55 (br
d, J = 7.1 Hz, 2H), 7.49 (t, J = 8.0 Hz, 1H), 7.44 (br t, J = 7.4 Hz,
1H), 7.32 (br t, J = 7.8 Hz, 2H) ppm; 13C{1H} NMR (100 MHz,
CDCl3): δ 185.0, 184.8, 147.5, 138.2, 136.4, 133.9, 132.9, 129.2,
128.6, 128.0, 126.5, 123.4, 85.5 ppm; HRMS-EI m/z: [M]+ calcd for
C15H9N3O4, 295.0593; found, 295.0598.
1-([1,1′-Biphenyl]-4-yl)-2-diazo-3-phenylpropane-1,3-dione (1i).
The titled compound was prepared from 5i (0.271 g, 0.9 mmol) by
following the general procedure. Purification by chromatography
(hexane/EtOAc = 20:1, 5:1) provided 1i as yellow oil (0.297 g,
quant.). IR (neat): 3058, 3031, 2111, 1652, 1646, 1635, 1578, 1296,
902, 858, 743, 696 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.66 (br d,
J = 8.2 Hz, 2H), 7.65 (br, d, J = 7.3 Hz, 2H), 7.55 (t, J = 8.2 Hz, 2H),
7.54 (t, J = 6.8 Hz, 2H), 7.47−7.36 (m, 4H), 7.31 (t, J = 7.8 Hz, 2H)
ppm; 13C{1H} NMR (100 MHz, CDCl3): δ 186.4, 185.9, 145.3,
139.6, 136.9, 135.5, 132.5, 129.0, 128.8, 128.3, 128.3, 128.2, 127.1,
126.8, 84.3 ppm; HRMS-EI m/z: [M]+ calcd for C21H14N2O2,
326.1055; found, 326.1051.
2-Diazo-1-phenyl-3-(p-tolyl)propane-1,3-dione (1j). The titled
compound was prepared from 5j (0.323 g, 1.36 mmol) by following
the general procedure. Purification by chromatography (hexane/
EtOAc = 20:1, 5:1) provided 1j as yellow oil (0.357 g, quant.). IR
(neat): 3082, 2981, 2110, 1651, 1645, 1601, 1289, 967, 861, 828, 790
cm−1; 1H NMR (400 MHz, CDCl3): δ 7.58 (dd, J = 7.8, 1.4 Hz, 2H),
7.49 (br d, J = 8.2 Hz, 2H), 7.45 (tt, J = 7.5, 1.1 Hz, 1H), 7.36−7.29
(m, 2H), 7.12 (d, J = 8.0 Hz, 2H), 2.33 (s, 3H) ppm; 13C{1H} NMR
(100 MHz, CDCl3): δ 186.5, 186.0, 143.5, 136.9, 134.1, 132.5, 128.9,
128.5, 128.3, 128.2, 83.7, 21.5 ppm; HRMS-EI m/z: [M]+ calcd for
C16H12N2O2, 264.0899; found, 264.0892.
1-(4-Chlorophenyl)-2-diazo-3-phenylpropane-1,3-dione (1k).
The titled compound was prepared from 5k (0.302 g, 1.17 mmol)
by following the general procedure. Purification by chromatography
(hexane/EtOAc = 40:1, 5:1) provided 1k as yellow oil (0.336 g,
quant.). IR (neat): 3061, 2111, 1645, 1589, 1293, 900, 857, 837, 748,
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747, 718 cm−1; H NMR (400 MHz, CDCl3): δ 7.57 (br d, J = 7.8
Hz, 2H), 7.45 (br t, J = 7.4 Hz, 1H), 7.33 (t, J = 7.8 Hz, 2H), 7.16
(dd, J = 8.1, 1.7 Hz, 1H), 7.08 (d, J = 1.7 Hz, 1H), 6.69 (d, J = 8.1 Hz,
1H), 5.97 (s, 2H) ppm; 13C{1H} NMR (100 MHz, CDCl3): δ 186.5,
184.6, 151.4, 147.8, 137.0, 132.5, 131.0, 128.3, 128.2, 124.7, 108.5,
107.7, 101.8, 83.5 ppm; HRMS-EI m/z: [M]+ calcd for C16H10N2O4,
294.0641; found, 294.0637.
2-Diazo-1-(naphthalen-2-yl)-3-phenylpropane-1,3-dione (1o).
The titled compound was prepared from 5o (323.7 mg, 1.18
mmol) by following the general procedure. Purification by
chromatography (hexane/EtOAc = 20:1, 5:1) provided 1o as yellow
oil (350.6 mg, 99%). IR (neat): 3058, 2113, 1644, 1634, 1295, 906,
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882, 756 cm−1; H NMR (400 MHz, CDCl3): δ 8.10 (br s, 1H),
7.82−7.76 (m, 3H), 7.65 (dd, J = 8.4, 1.7 Hz, 1H), 7.61 (br d, J = 7.2
Hz, 2H), 7.55 (br t, J = 7.4 Hz, 1H), 7.49 (br t, J = 7.7 Hz, 1H), 7.35
(br t, J = 7.4 Hz, 1H), 7.26 (t, J = 8.4 Hz, 2H) ppm; 13C{1H} NMR
(100 MHz, CDCl3): δ 186.4, 186.2, 137.0, 135.1, 134.1, 132.5, 132.0,
129.8, 129.1, 128.3, 128.2 (×3), 127.7, 126.8, 124.2, 84.4 ppm;
HRMS-EI m/z: [M]+ calcd for C19H12N2O2, 300.0899; found,
300.0905.
2-Diazo-1-(3-methoxyphenyl)-3-(p-tolyl)propane-1,3-dione (1p).
The titled compound was prepared from 5p (265.4 mg, 0.989 mmol)
by following the general procedure. Purification by chromatography
(hexane/EtOAc = 40:1, 5:1) provided 1p as yellow oil (288.2 mg,
99%). IR (neat): 3060, 2941, 2992, 2114, 1644, 1634, 1606, 1289,
830, 775, 746 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.49 (d, J = 8.1
Hz, 2H), 7.22 (t, J = 7.8 Hz, 1H), 7.16−7.09 (m, 4H), 6.98 (dd, J =
8.1, 1.8 Hz, 1H), 3.76 (s, 3H), 2.34 (s, 3H) ppm; 13C{1H} NMR (100
MHz, CDCl3): δ 186.2, 186.1, 159.4, 143.5, 138.2, 134.2, 129.3,
128.9, 128.5, 120.7, 118.9, 112.8, 83.8, 55.3, 21.6 ppm; HRMS-EI m/
z: [M]+ calcd for C17H14N2O3, 294.1104; found, 294.1099.
2-Diazo-1-(3-nitrophenyl)-3-(p-tolyl)propane-1,3-dione (1q).
The titled compound was prepared from 5q (98.5 mg, 0.348
mmol) by following the general procedure. Purification by
chromatography (hexane/EtOAc = 20:1, 4:1) provided 1q as yellow
oil (105.4 mg, 98%). IR (neat): 3038, 2956, 2120, 1644, 1607, 1531,
1349, 1305, 741, 713 cm−1; 1H NMR (400 MHz, CDCl3): δ 8.34 (t, J
J
J. Org. Chem. XXXX, XXX, XXX−XXX