The Journal of Organic Chemistry
Note
yellow solid (63.3 mg, 73%); mp 82−84 °C (lit.22 mp 86−87 °C); IR
1-(2-Fluorophenyl)-2-phenylethane-1,2-dione (2s).26 Purified by
column chromatography (petroleum ether/EtOAc, 10:1) as a pale
yellow solid (49.9 mg, 73%); mp 60−62 °C (lit.26 mp 63−64 °C); IR
1
(KBr) ν 1670 (CO) cm−1; H NMR (CDCl3, 500 MHz) δ 7.98
(dd, J1 = 8.5 Hz, J2 = 1.5 Hz, 2H), 7.86 (d, J = 8.5 Hz, 2H), 7.69−7.68
(m, 3H), 7.56 (t, J = 8.0 Hz, 2H); MS (EI, 70 eV) m/z (%) 288 (1)
[M+], 105 (100).
1
(KBr) ν 1682 (CO) cm−1; H NMR (CDCl3, 500 MHz) δ 8.09−
8.05 (m, 1H), 8.00−7.98 (m, 2H), 7.70−7.64 (m, 2H), 7.56−7.53 (m,
2H), 7.38−7.35 (m, 1H), 7.16−7.12 (m, 1H); 13C{1H} (CDCl3, 125
MHz) δ 193.1, 191.9, 162.9 (d, J = 257.5 Hz), 136.8 (d, J = 8.8 Hz),
134.7, 132.1 (d, J = 2.5 Hz), 130.8 (d, J = 1.3 Hz), 129.9, 129.0, 125.0
(d, J = 3.8 Hz), 122.4 (d, J = 10.0 Hz), 116.7 (d, J = 21.3 Hz); MS (EI,
70 eV) m/z (%) 228 (3) [M+], 105 (100).
1-(3-Nitrophenyl)-2-phenyl-1,2-ethanedione (2j).26 Purified by
column chromatography (petroleum ether/EtOAc, 10:1) as a pale
yellow solid (61.2 mg, 80% from 1j; 30.6 mg, 40% from 1k); mp 118−
120 °C (lit.26 mp 119−121 °C); IR (KBr) ν 1674 (CO) cm−1; H
1
NMR (CDCl3, 400 MHz) δ 8.83 (t, J = 2.0 Hz, 1H), 8.53−8.50 (m,
1H), 8.34−8.31 (m, 1H), 8.03−8.00 (m, 2H), 7.77−7.70 (m, 2H),
7.58−7.54 (m, 2H); MS (EI, 70 eV) m/z (%) 255 (3) [M+], 105
(100).
1-(Naphthalen-1-yl)-2-phenylethane-1,2-dione (2t).30 Purified by
column chromatography (petroleum ether/EtOAc, 10:1) as a pale
yellow solid (39.8 mg, 51%); mp 99−100 °C (lit.30 mp 101.5−102
°C); IR (KBr) ν 1651 (CO) cm−1; 1H NMR (CDCl3, 500 MHz) δ
9.35 (d, J = 9.0 Hz, 1H), 8.11 (d, J = 8.5 Hz, 1H), 8.06 (d, J = 7.5 Hz,
2H), 7.95−7.93 (m, 2H), 7.77−7.74 (m, 1H), 7.68−7.62 (m, 2H),
7.54−7.46 (m, 3H); 13C{1H} NMR (CDCl3, 125 MHz) δ 197.1,
194.5, 135.9, 135.0, 134.7, 134.0, 133.3, 130.9, 129.9, 129.4, 129.0,
128.8, 128.6, 127.1, 125.8, 124.4; MS (EI, 70 eV) m/z (%) 260 (4)
[M+], 105 (100).
1-Phenyl-2-(2-thienyl)-1,2-dione (2l).21 Purified by column chro-
matography (petroleum ether/EtOAc, 10:1) as a pale yellow solid
(37.0 mg, 57%); mp 59−61 °C (lit.21 mp 62−63 °C); IR (KBr) ν
1
1649 (CO) cm−1; H NMR (CDCl3, 400 MHz) δ 8.06−8.04 (m,
2H), 7.85−7.81 (m, 2H), 7.69−7.64 (m, 1H), 7.54−7.50 (m, 2H),
7.21−7.18 (m, 1H); MS (EI, 70 eV) m/z (%) 216 (3) [M+], 105
(100).
1-Phenylpropane-1,2-dione (2m).27 Purified by column chroma-
tography (petroleum ether/EtOAc, 10:1) as a yellow oil (28.0 mg,
63%); IR (neat) ν 1674 (CO) cm−1; 1H NMR (CDCl3, 500 MHz)
δ 8.03 (dd, J1 = 8.0 Hz, J2 = 1.5 Hz, 2H), 7.68−7.64 (m, 1H), 7.53−
7.50 (m, 2H), 2.54 (s, 3H); MS (EI, 70 eV) m/z (%) 148 (4) [M+].
1-(3-Methylphenyl)-2-phenyl-1,2-ethanedione (2n).28 Purified by
column chromatography (petroleum ether/EtOAc, 10:1) as a yellow
solid (42.4 mg, 63%); mp 54−56 °C (lit.28 mp 56−57 °C); IR (KBr) ν
1-(4-Fluorophenyl)-2-(p-tolyl)ethane-1,2-dione (2u). Purified by
column chromatography (petroleum ether/EtOAc, 10:1) as a white
solid (49.4 mg, 68%); mp 89−91 °C; IR (KBr) ν 1672 (CO) cm−1;
1H NMR (CDCl3, 400 MHz) δ 7.96−7.92 (m, 2H), 7.79 (dd, J1 = 2.0
Hz, J2 = 8.0 Hz, 2H), 7.24 (dd, J1 = 2.0 Hz, J2 = 8.0 Hz, 2H), 7.12−
7.08 (m, 2H), 2.36 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ
192.8, 191.9, 165.7 (d, J = 256 Hz), 145.4, 131.7 (d, J = 10.0 Hz),
129.5, 129.0, 128.9, 115.3 (d, J = 22.0 Hz); MS (EI, 70 eV) m/z (%)
242 (2) [M+], 119 (100); HRMS (EI) for C15H11FO2 [M+] calcd
242.0743, found 242.0752; Anal. Calcd for C15H11FO2, C 74.37, H
4.58; found, C 74.60, H 4.52.
1
1672 (CO) cm−1; H NMR (CDCl3, 500 MHz) δ 7.98 (d, J = 8.5
Hz, 2H), 7.89 (d, J = 8.0 Hz, 2H), 7.67 (t, J = 7.5 Hz, 1H), 7.52 (t, J =
8.0 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 2.45 (s, 3H); MS (EI, 70 eV)
m/z (%) 224 (3) [M+], 119 (100).
1-(2-Chlorophenyl)-2-p-tolylethane-1,2-dione (2v).31 Purified by
column chromatography (petroleum ether/EtOAc, 10:1) as a pale
yellow solid (46.6 mg, 60%); mp 80−81 °C (lit.31 mp 82−83 °C); IR
1-[1,1′-Biphenyl]-2-yl-2-phenyl-1,2-ethanedione (2o). Purified by
column chromatography (petroleum ether/EtOAc, 10:1) as a pale
yellow solid (52.4 mg, 61%); mp 78−80 °C; IR (KBr) ν 1672 (CO)
1
(KBr) ν 1673 (CO) cm−1; H NMR (CDCl3, 500 MHz) δ 7.96−
1
cm−1; H NMR (CDCl3, 500 MHz) δ 7.96 (dd, J1 = 8.0 Hz, J2 = 1.5
7.91 (m, 3H), 7.57−7.35 (m, 5H), 2.47 (s, 3H); MS (EI, 70 eV) m/z
(%) 258 (2) [M+], 119 (100).
Hz, 1H), 7.79−7.78 (m, 2H), 7.67−7.64 (m, 1H), 7.57−7.54 (m, 2H),
7.42 (dd, J1 = 7.5 Hz, J2 = 0.5 Hz, 1H), 7.38−7.35 (m, 2H), 7.22−7.20
(m, 2H), 7.07−7.04 (m, 3H); 13C{1H} NMR (125 MHz, CDCl3) δ
195.7, 191.4, 143.6, 139.8, 135.2, 133.9, 132.9, 132.8, 130.6, 130.5,
129.8, 128.3, 128.1, 128.0, 127.7; MS (EI, 70 eV) m/z (%) 286 (3)
[M+], 105 (100); HRMS (EI) for C20H14O2 [M+] calcd 286.0994,
found 286.0986; Anal. Calcd for C20H14O2, C 83.90, H 4.93; found, C
83.68, H 4.97.
1-(4-Chlorophenyl)-2-(4-fluorophenyl)-1,2-ethanedione (2x).24
Purified by column chromatography (petroleum ether/EtOAc, 10:1)
as a white solid (57.5 mg, 73%); mp 143−145 °C (lit.24 mp 144−146
°C); IR (KBr) ν 1662 (CO) cm−1; 1H NMR (CDCl3, 400 MHz) δ
8.04−7.99 (m, 2H), 7.94−7.91 (m, 2H), 7.51−7.48 (m, 2H), 7.22−
7.19 (m, 2H); 13C{1H} (100 MHz, CDCl3) δ 192.5, 192.0, 166.9 (d, J
= 257.0 Hz), 141.8, 132.8 (d, J = 10.0 Hz), 131.2 (d, J = 2.0 Hz),
129.5, 129.34, 129.31, 116.5 (d, J = 22.0 Hz); MS (EI, 70 eV) m/z (%)
262 (4) [M+], 123 (100).
1-(4-Chlorophenyl)-2-phenylethane-1,2-dione (2p).26 Purified by
column chromatography (petroleum ether/EtOAc, 10:1) as a pale
yellow solid (58.7 mg, 80%); mp 72−75 °C (lit.26 mp 75−76 °C); IR
1-(4-Bromophenyl)-2-(4-methylphenyl)-1,2-dione (2y). Purified
by column chromatography (petroleum ether/EtOAc, 10:1) as a
pale yellow solid (64.6 mg, 71%); mp 131−133 °C; IR (KBr) ν 1664
1
(KBr) ν 1668 (CO) cm−1; H NMR (CDCl3, 500 MHz) δ 7.98
(dd, J1 = 8.0 Hz, J2 = 1.0 Hz, 2H), 7.94 (dd, J1 = 7.0 Hz, J2 = 2.0 Hz,
2H), 7.69 (t, J = 7.0 Hz, 1H), 7.56−7.50 (m, 4H); MS (EI, 70 eV) m/
z (%) 244 (2) [M+], 105 (100).
1
(CO) cm−1; H NMR (CDCl3, 500 MHz) δ 7.85−7.84 (m, 4H),
7.68−7.66 (m, 2H), 7.33 (d, J = 8.0 Hz, 2H), 2.46 (s, 3H); 13C{1H}
NMR (125 MHz, CDCl3) δ 193.6, 193.5, 146.5, 132.4, 131.9, 131.3,
130.43, 130.38, 130.1, 129.8, 22.0; MS (EI, 70 eV) m/z (%) 302 (1)
[M+], 119 (100); HRMS (EI) for C15H11BrO2 [M+] calcd 301.9942,
found 301.9934; Anal. Calcd for C15H11BrO2, C 59.43, H 3.66; found,
C 59.26, H 3.62.
1-(4-Isopropylphenyl)-2-phenylethane-1,2-dione (2q).29 Purified
by column chromatography (petroleum ether/EtOAc, 10:1) as a pale
1
yellow liquid (44.6 mg, 59%); IR (KBr) ν 1673 (CO) cm−1; H
NMR (CDCl3, 500 MHz) δ 8.00−7.98 (m, 2H), 7.92 (d, J = 8.5 Hz,
2H), 7.66 (t, J = 7.5 Hz, 1H), 7.52 (t, J = 8.0 Hz, 2H), 7.38 (d, J = 8.0
Hz, 2H), 3.04−2.96 (m, 1H), 1.29 (d, J = 7.0 Hz, 6H); 13C{1H}
(CDCl3, 125 MHz) δ 194.8, 194.3, 156.8, 134.8, 133.2, 131.0, 130.2,
129.9, 129.0, 127.2, 34.5, 23.5; MS (EI, 70 eV) m/z (%) 252 (4) [M+],
105 (100).
1-(4-Bromophenyl)-2-(4-fluorophenyl)ethane-1,2-dione (2z). Pu-
rified by column chromatography (petroleum ether/EtOAc, 10:1) as a
pale yellow solid (69.1 mg, 75%); mp 160−162 °C; IR (KBr) ν 1663
1
(CO) cm−1; H NMR (CDCl3, 400 MHz) δ 8.04−8.00 (m, 2H),
7.86−7.83 (m, 2H), 7.69−7.66 (m, 2H), 7.23−7.17 (m, 2H); 13C{1H}
NMR (100 MHz, CDCl3) δ 192.8, 192.0, 166.9 (d, J = 257.0 Hz),
132.8 (d, J = 10.0 Hz), 132.5, 131.6, 131.3, 130.7, 129.3 (d, J = 3.0
Hz), 116.5 (d, J = 22.0 Hz); MS (EI, 70 eV) m/z (%) 306 (2) [M+],
123 (100); HRMS (EI) for C14H8BrFO2 [M+] calcd 305.9692, found
305.9683; Anal. Calcd for C14H8BrFO2, C 54.75, H 2.63; found, C
54.56, H, 2.67.
1-(3,4-Dichlorophenyl)-2-phenylethane-1,2-dione (2r). Purified
by column chromatography (petroleum ether/EtOAc, 10:1) as a
pale yellow solid (36.1 mg, 43%); mp 97−99 °C; IR (KBr) ν 1664
1
(CO) cm−1; H NMR (CDCl3, 500 MHz) δ 8.10 (d, J = 2.0 Hz,
1H), 7.98(dd, J1 = 8.0 Hz, J2 = 0.5 Hz, 2H), 7.82 (dd, J1 = 8.5 Hz, J2 =
1.0 Hz, 1H), 7.72−7.69 (m, 1H), 7.20 (d, J = 8.0 Hz, 1H), 7.55 (t, J =
8.0 Hz, 2H); 13C{1H} (CDCl3, 125 MHz) δ 193.1, 191.8, 139.8, 135.3
(2C), 134.0, 132.6, 131.6, 131.2, 130.0, 129.2, 128.8; HRMS (EI) for
C14H8Cl2O2 [M+] calcd 277.9901, found 277.9910; Anal. Calcd for
C14H8Cl2O2, C 60.24, H 2.89; found, C 60.42, H 2.92.
Procedure for the Synthesis of Diketo Ester 5 (5′) from
Oxiranyl Carboxylates 3 Mediated by Selectfluor. The
procedure is the same as for the preparation of 2.
F
J. Org. Chem. XXXX, XXX, XXX−XXX