10.1002/ejoc.201901679
European Journal of Organic Chemistry
FULL PAPER
– 7.48 (m, 2H), 7.39 – 7.32 (m, 2H), 7.32 – 7.23 (m, 4H), 7.19 – 7.16 (m,
2H), 6.96 (s, 1H), 3.68 (d, J = 14.0 Hz, 1H), 3.55 (d, J = 14.0 Hz, 1H) ppm;
13C-NMR (101 MHz, CDCl3): δ = 169.4 (CO) , 151.2 (C) , 139.7 (C) , 134.9
(C) , 134.28 (C), 134.19 (CH), 130.15 (q, J = 32.1 Hz) (C), 129.5 (CH),
128.96 (2xCH) , 128.68 (CH) , 128.51 (CH) , 127.34 (q, J = 3.9 Hz) (CH),
126.02 (C) , 125.94 (CH), 125.35 (2xCH), 123.94 (q, J = 272.4 Hz) (CF3),
123.93 (q, J = 4.0 Hz) (C), 122.7 (CH) , 89.2 (C) , 46.3 (CH2) ppm; HRMS
(ESI-TOF) m/z calculated for C22H16O2F3 [M+ + H] 369.1102, found
335.1103; IR (ATR): 휈 = 1787, 1623, 1492, 1468, 1383, 1279, 1174, 1135
cm-1.
7.94 (d, J = 8.7 Hz, 2H), 7.69 (td, J = 7.0, 1.2 Hz, 2H), 7.65 – 7.62 (m, 1H),
7.49 – 7.39 (m, 3H), 7.19 (d, J = 8.0 Hz, 2H), 7.14 (d, J = 8.7 Hz, 2H), 3.83
(d, J = 13.9 Hz, 1H), 3.64 (d, J = 13.9 Hz, 1H), 2.34 (s, 3H) ppm; 13C-NMR
(101 MHz, CDCl3): δ = 169.3 (CO), 151.4 (C), 147.1 (C), 141.9 (C), 138.7
(C), 136.5 (C), 134.4 (CH) , 131.6 (2xCH), 129.68 (2xCH), 129.60 (CH),
126.06 (CH), 125.8 (C), 125.2 (2xCH), 123.1 (2xCH), 122.6 (CH), 89.0 (C),
46.1 (CH2), 21.1 (CH3) ppm; HRMS (ESI-TOF) m/z calculated for
C22H18NO4 [M+ + H] 360.1236, found 360.1223; IR (ATR): 휈 =3052, 1768,
1576, 1542, 1415, 1335, 1190, 778 cm-1.
3-(4-Methoxyphenyl)-3-(4-nitrobenzyl)isobenzofuran-1(3H)-one (3cb):
Following the general procedure with substrates 1c and 4-nitroaniline (2b),
compound 3cb was obtained after column chromatography (from 90:10 to
70:30 hexane/EtOAc) as a yellow sticky oil (92.3 mg, 0.25 mmol, 82%).
TLC (hexane/EtOAc 70:30): Rf = 0.35; 1H-NMR (300 MHz, CDCl3): δ =
7.93 (d, J = 8.7 Hz, 2H), 7.74 – 7.66 (m, 2H), 7.60 (dt, J = 8.0, 0.9 Hz, 1H),
7.49 – 7.41 (m, 3H), 7.13 (d, J = 8.7 Hz, 2H), 6.89 (d, J = 8.9 Hz, 2H), 3.82
(d, J = 14.0 Hz, 1H), 3.79 (s, 3H), 3.62 (d, J = 13.9 Hz, 1H) ppm; 13C-NMR
(101 MHz, CDCl3): δ = 169.2 (CO), 159.8 (C), 151.4 (C), 147.1 (C), 141.9
(C), 134.3 (CH), 131.60 (2xCH) , 131.40 (C), 129.6 (CH), 126.8 (2xCH),
126.07 (CH), 125.9 (C), 123.1 (2xCH), 122.6 (CH), 114.3 (CH), 88.9 (C),
55.5 (CH3), 46.2 (CH2) ppm; HRMS (ESI-TOF) m/z calculated for
C21H18NO5 [M+ + H] 376.1179, found 376.1177; IR (ATR): 휈 =3098, 1777,
1596, 1539, 1398, 1345, 1190, 1002, 767 cm-1.
3-(2-Nitrobenzyl)-3-phenylisobenzofuran-1(3H)-one (3ak): Following
the general procedure with substrates 1a and 2-nitroaniline (2k),
compound 3ak was obtained after column chromatography (from 90:10 to
70:30 hexane/EtOAc) as a yellow solid (1.384 g, 4.00 mmol, 80%). TLC
(hexane/EtOAc 70:30): Rf = 0.39; 1H-NMR (300 MHz, CDCl3): δ = 7.68 –
7.60 (m, 4H), 7.60 – 7.53 (m, 2H), 7.45 – 7.31 (m, 6H), 7.29 – 7.21 (m, 1H),
4.38 (d, J = 14.5 Hz, 1H), 4.11 (d, J = 14.5 Hz, 1H) ppm; 13C-NMR (75
MHz, CDCl3): δ = 169.1 (CO), 150.8 (C), 150.1 (C), 139.7 (C), 134.6 (CH),
134.2 (CH), 132.5 (CH), 129.51 (CH), 128.97 (2xCH), 128.93 (C), 128.7
(CH), 128.37 (CH), 125.70 (CH), 125.52 (C), 125.12 (2xCH), 124.8 (CH),
122.8 (CH), 89.2 (C), 41.4 (CH2) ppm; HRMS (ESI-TOF) m/z calculated
for C21H16NO4 [M+ + H] 346.1079, found 346.1073; IR (ATR): 휈 = 2952,
1762, 1602,1520, 1345, 1170, 776 cm-1.
3-Iodo-4-((3-oxo-1-phenyl-1,3-dihydroisobenzofuran-1-
3-(4-Chlorophenyl)-3-(4-nitrobenzyl)isobenzofuran-1(3H)-one (3db):
Following the general procedure with substrates 1d and 4-nitroaniline (2b),
compound 3db was obtained after column chromatography (from 90:10 to
70:30 hexane/EtOAc) as a yellow solid (80.9mg, 0.21 mmol, 71%). TLC
(hexane/EtOAc 70:30): Rf = 0.36; 1H-NMR (400 MHz, CDCl3): δ = 7.98 –
7.94 (m, 2H), 7.71 (ddd, J = 7.4, 6.4, 1.3 Hz, 2H), 7.63 (d, J = 7.9 Hz, 1H),
7.52 – 7.47 (m, 3H), 7.39 – 7.33 (m, 2H), 7.14 (d, J = 8.7 Hz, 2H), 3.80 (d,
J = 13.9 Hz, 1H), 3.62 (d, J = 13.9 Hz, 1H). ppm; 13C-NMR (101 MHz,
CDCl3): δ = 168.9 (CO), 150.8 (C), 147.2 (C), 141.3 (C), 138.2 (C), 134.9
1 (C), 134.58 (CH), 131.6 (2xCH), 129.93 (CH), 129.25 (2xCH), 126.73
(2xCH), 126.32 (2xCH), 125.7 (C), 123.3 (2xCH), 122.4 (CH), 88.4 (C),
46.2 (CH2) ppm; HRMS (ESI-TOF) m/z calculated for C21H15NO4Cl [M+ +
H] 380.0690, found 380.0683; IR (ATR): 휈 = 1782, 1596, 1545, 1405, 1342,
1190, 1010, 778 cm-1.
yl)methyl)benzonitrile (3al): Following the general procedure with
substrates 1a and 4-amino-3-iodobenzonitrile (2l), compound 3al was
obtained after column chromatography (from 90:10 to 70:30
hexane/EtOAc) as a yellow solid (70.4 mg, 0.17 mmol, 52%). TLC
(hexane/EtOAc 80:20): Rf =0.32; 1H-NMR (400 MHz, CDCl3): δ = 7.98 (d,
J = 1.7 Hz, 1H), 7.78 (ddd, J = 7.0, 1.9, 1.1 Hz, 2H), 7.69 (td, J = 7.5, 1.1
Hz, 1H), 7.59 – 7.53 (m, 2H), 7.50 (td, J = 7.5, 0.9 Hz, 1H), 7.41 – 7.31 (m,
4H), 7.22 (d, J = 8.1 Hz, 1H), 4.02 (d, J = 14.7 Hz, 1H), 3.84 (d, J = 14.7
Hz, 1H) ppm; 13C-NMR (101 MHz, CDCl3): δ = 169.0 (CO), 151.0 (C),
143.25 (C), 142.61 (CH), 139.2 (C), 134.2 (CH), 131.11 (CH), 131.06 (CH),
129.7 (CH), 128.94 (2xCH), 128.7 (CH), 125.9 (CH), 125.4 (C), 125.2
(2xCH), 123.3 (CH), 116.7 (C), 112.6 (CN), 102.6 (C), 89.2 (C), 50.0 (CH2)
ppm; HRMS (ESI-TOF) m/z calculated for C22H15INO2 [M+ + H] 452.0147,
found 452.0159; IR (ATR): 휈 = 2952, 2225, 1762, 1602,1520, 1242, 1170,
776 cm-1.
3-(4-Nitrobenzyl)-3-(thiophen-2-yl)isobenzofuran-1(3H)-one
(3eb):
Following the general procedure with substrates 1e and 4-nitroaniline (2b),
compound 3eb was obtained after column chromatography (from 90:10 to
70:30 hexane/EtOAc) as a pale yellow solid (66.5 mg, 0.19 mmol, 63%).
TLC (hexane/EtOAc 70:30): Rf = 0.38; 1H-NMR (400 MHz, CDCl3): δ =
7.96 (d, J = 8.7 Hz, 2H), 7.75 – 7.68 (m, 2H), 7.61 (dt, J = 7.7, 0.9 Hz, 1H),
7.50 (td, J = 7.5, 0.9 Hz, 1H), 7.33 (dd, J = 5.1, 1.2 Hz, 1H), 7.15 (d, J =
8.7 Hz, 2H), 7.09 (dd, J = 3.6, 1.2 Hz, 1H), 6.99 (dd, J = 5.1, 3.6 Hz, 1H),
3.91 (d, J = 13.8 Hz, 1H), 3.67 (d, J = 13.9 Hz, 1H) ppm; 13C-NMR (101
MHz, CDCl3): δ = 168.6 (CO), 150.4 (C), 147.2 (C), 142.8 (C), 141.2 (C),
134.5 (CH), 131.6 (2xCH), 130.1 (CH), 127.3 (CH), 126.54 (CH), 126.15
(CH), 125.93 (C), 125.66 (CH), 123.2 (2xCH), 122.6 (CH), 87.0 (C), 47.0
(CH2) ppm; HRMS (ESI-TOF) m/z calculated for C19H14NO4S [M+ + H]
352.0644, found 352.0635; IR (ATR): 휈 =1780, 1603, 1537, 1345, 1250,
1183, 778 cm-1.
Methyl
3-((3-oxo-1-phenyl-1,3-dihydroisobenzofuran-1-
yl)methyl)thiophene-2-carboxylate (3am): Following the general
procedure with substrates 1a and methyl 3-aminothiophene-2-carboxylate
(2m), compound 3am was obtained after column chromatography (from
95:5 to 80:20 hexane/EtOAc) as a yellow solid (57 mg, 0.16 mmol, 52%).
TLC (hexane/EtOAc 80:20): Rf = 0.43; 1H-NMR (400 MHz, CDCl3): δ =
7.69 – 7.60 (m, 4H), 7.54 (td, J = 7.6, 1.2 Hz, 1H), 7.41 – 7.33 (m, 4H),
7.32 – 7.27 (m, 1H), 7.25 (d, J = 5.1 Hz, 1H), 7.01 (d, J = 5.1 Hz, 1H), 4.52
(d, J = 14.4 Hz, 1H), 4.06 (d, J = 14.4 Hz, 1H), 3.80 (s, 3H) ppm; 13C-NMR
(101 MHz, CDCl3): δ = 13C NMR (101 MHz, CDCl3) δ 169.8 (CO), 163.0
(CO2Me), 151.7 (C), 142.8 (C), 140.2 (C), 133.7 (CH), 131.7 (CH), 130.3
(CH), 129.2 (CH), 128.79 (2xCH2), 128.51 (C), 128.38 (CH), 125.44 (C),
125.41(CH), 125.16 (2xCH), 123.2 (CH), 90.0 (C), 51.9 (CH3), 38.3 (CH2)
ppm; HRMS (ESI-TOF) m/z calculated for C21H17O4S [M+ + H] 365.0848,
found 365.0845; IR (ATR): 휈 = 3061, 3029, 2995, 1780, 1707, 1603, 1537,
1437, 1416, 1257, 1191 cm-1.
7-Methyl-3-(4-nitrobenzyl)-3-phenylisobenzofuran-1(3H)-one
(3fb):
Following the general procedure with substrates 1f and 4-nitroaniline (2b),
compound 3fb was obtained after column chromatography (from 90:10 to
70:30 hexane/EtOAc) as an off white solid (77.6 mg, 0.22 mmol, 72%).
TLC (hexane/EtOAc 70:30): Rf = 0.46; 1H-NMR (300 MHz, CDCl3): δ =
7.96 (d, J = 8.7 Hz, 2H), 7.60 – 7.49 (m, 3H), 7.46 (dt, J = 7.7, 0.8 Hz, 1H),
7.44 – 7.27 (m, 3H), 7.21 (d, J = 7.4 Hz, 1H), 7.16 (d, J = 8.7 Hz, 2H), 3.81
(d, J = 13.9 Hz, 1H), 3.63 (d, J = 13.9 Hz, 1H), 2.54 (s, 3H) ppm; 13C-NMR
3-(4-Nitrobenzyl)-3-(p-tolyl)isobenzofuran-1(3H)-one (3bb): Following
the general procedure with substrates 1b and 4-nitroaniline (2b),
compound 3bb was obtained after column chromatography (from 90:10 to
70:30 hexane/EtOAc) as a pale yellow solid (82.6 mg, 0.23 mmol, 75%).
TLC (hexane/EtOAc 70:30): Rf = 0.38; 1H-NMR (400 MHz, CDCl3): δ =
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