The Journal of Organic Chemistry
Note
(m, 2H), 8.24−8.31 (m, 3H); 13C NMR (125 MHz, DMSO-d6) δ
122.6, 126.8, 129.2, 130.8, 133.9, 135.2, 137.5, 142.4, 167.0, 167.8,
168.3; EI-MS¯ m/z calcd for C11H8NO5 234.0402 [M − H]¯, found
234.0409.
(E)-5-Carbomethoxy-2-carboxycinamic Acid (9-CA). Yield 151 mg
(83%); colorless solid. Rf (20% MeOH/EtOAc): 0.4; mp 198−200 °C;
IR (KBr) cm−1 2900−2600 (br), 1734, 1687, 1626; 1H NMR
(DMSO-d6, 400 MHz) δ 3.89 (s, 3H), 6.45 (d, J = 16.0 Hz, 1H),
7.99−8.02 (m, 2H), 8.22−8.26 (m, 2H); 13C NMR (DMSO-d6, 125
MHz) δ 53.1, 123.0, 128.7, 130.4, 131.3, 133.1, 135.5, 135.7, 142.1,
165.8, 167.6, 168.0; ESI-MS¯ m/z calcd for C12H9O6 249.0399 [M −
H]¯, found 249.0398.
o-Phthalic Acid (18-A).21 Yield 148 mg (78%); colorless solid. Rf
(25% MeOH/EtOAc): 0.2; 1H NMR (500 MHz, DMSO-d6) δ 7.56−
7.60 (m, 2H), 7.64−7.68 (m, 2H).
6-Hydroxy-1,4-naphthoquinone (19-Q).22 Yield 24 mg (15%); red
solid. Rf (5% EtOAc/pet. ether): 0.4; 1H NMR (400 MHz,
CDCl3+CD3OD) δ 6.84 (s, 2H), 7.08 (dd, J1 = 8.4 Hz, J2 = 2.5 Hz,
1H), 7.33 (d, J = 2.5 Hz, 1H), 7.91 (d, J = 8.7 Hz, 1H).
5-Oxo-3-phenyl-2,5-dihydro-2-furanacetic Acid (20-LA). Yield 65
mg (23%); colorless solid. Rf (25% EtOAc/pet. ether): 0.4; mp 122−
124 °C; IR (KBr) cm−1 3100−2900 (br), 1729, 1619, 1573; 1H NMR
(400 MHz, CDCl3) δ 2.55−2.59 (m, 1H), 2.97−3.02 (m, 1H), 5.91−
5.93 (m, 1H), 6.34 (d, J = 1.6 Hz, 1H), 7.47−7.51 (m, 5H); 13C NMR
(125 MHz, CDCl3) δ 38.5, 77.9, 114.9, 127.1, 129.3, 129.5, 131.7,
166.3, 171.9, 173.9; EI-MS¯ m/z calcd for C12H9O4 217.0500 [M −
H]¯, found 217.0507.
(E)-2-Carboxy-5-(4-tolyl)cinnamic Acid (10-CA). Yield 181 mg
(95%); colorless solid. Rf (EtOAc): 0.4; mp 239−242 °C; IR (KBr)
cm−1 3000−2600 (br), 1705, 1683, 1631, 1602; 1H NMR (DMSO-d6,
400 MHz) δ 2.36 (s, 3H), 6.60 (d, J = 16.1 Hz, 1H), 7.31 (d, J = 8.2
Hz, 2H), 7.73 (d, J = 8.2 Hz, 2H), 7.78 (d, J = 8.2 Hz, 1H), 7.95 (d, J
= 8.2 Hz, 1H), 8.01 (s, 1H), 8.38 (d, J = 16.1 Hz, 1H); 13C NMR
(DMSO-d6, 125 MHz) δ 21.2, 122.3, 125.9, 127.4, 127.8, 129.9, 130.1,
131.6, 136.1, 136.3, 138.4, 143.2, 143.9, 168.0, 168.4; ESI-MS− m/z
calcd for C17H13O4 281.0813 [M − H]−, found 281.0813.
(E)-2-Carboxy-5-(4-anisyl)cinnamic Acid (11-CA). Yield 150 mg
(84%); colorless solid. Rf (10% MeOH/EtOAc): 0.4; mp 138−140 °C;
2,2′-Diphenic Acid (21-DA).23 Yield 79 mg (59%); colorless solid.
Rf (20% MeOH/EtOAc): 0.4; mp 251−254 °C; 1H NMR (DMSO-d6,
500 MHz) δ 7.15 (d, J = 7.4 Hz, 1H), 7.42 (t, J = 7.4 Hz, 1H), 7.53 (t,
J = 8.2 Hz, 1H), 7.87 (d, J = 8.2 Hz, 1H).
Dibenzo[b,d]pyrone (21-L).24 Yield 25 mg (23%); colorless solid.
Rf (5% EtOAc/pet. ether): 0.32; IR (KBr) cm−1 1729, 1606; 1H NMR
(400 MHz, CDCl3) δ 7.31−7.36 (m, 2H), 7.47 (dt, J1 = 7.8 Hz, J2 =
1.6 Hz, 1H), 7.57 (dt, J1 = 8.0 Hz, J2 = 1.0 Hz, 1H), 7.79−7.82 (m,
1H), 8.05 (dd, J1 = 8.0 Hz, J2 = 1.3 Hz, 1H), 8.11 (d, J = 8.0 Hz, 1H),
8.39 (dd, J1 = 8.2 Hz, J2 = 1.3 Hz, 1H); 13C NMR (125 MHz, CDCl3)
δ 117.8, 118.0, 121.2, 121.7, 122.7, 124.5, 128.8, 130.4, 130.6, 134.7,
134.8, 151.3, 161.2; EI-MS+ m/z calcd for C13H8O2 196.0524 [M]+,
found 196.0517.
1
IR (KBr) cm−1 3500−2500 (br), 1706, 1601; H NMR (400 MHz,
DMSO-d6) δ 3.81 (s, 3H), 6.59 (d, J = 16.0 Hz, 1H), 7.05 (d, J = 9.1
Hz, 2H), 7.75−7.80 (m, 3H), 7.95 (d, J = 8.2 Hz, 2H), 7.99 (s, 1H),
8.38 (d, J = 16.0 Hz, 1H); 13C NMR (125 MHz, DMSO-d6) δ 55.7,
114.9, 122.3, 125.7, 127.5, 128.9, 129.1, 131.2, 131.8, 136.4, 143.3,
143.7, 160.2, 168.0, 168.4; EI-MS¯ m/z calcd for C17H13O5 297.0763
[M − H]¯, found 297.0765.
2-(3-Oxo-1,3-dihydronaphtho[2,1-c]furan-1-yl)acetic Acid (22-
LA). Yield 105 mg (85%); colorless solid. Rf (10% MeOH/EtOAc):
0.3; mp 138−140 °C; IR (KBr) cm−1 3000−2700 (br), 2921, 1752,
(E)-2-Carboxy-5-(4-phenoxy)cinnamic Acid (12-CA). Yield 127 mg
(71%); colorless solid. mp 180−182 °C; Rf (10% MeOH/EtOAc): 0.5;
IR (KBr) cm−1 3100−2600, 1686, 1599; 1H NMR (500 MHz, DMSO-
d6) δ 6.57 (d, J = 16.0 Hz, 1H), 6.87 (d, J = 8.7 Hz, 2H), 7.66−7.73
(m, 3H), 7.93 (d, J = 8.7 Hz, 2H), 8.39 (d, J = 16.0 Hz, 1H); 13C
NMR (100 MHz, DMSO-d6) δ 116.3, 122.1, 125.4, 127.3, 128.7,
128.9, 129.6, 131.8, 136.4, 143.4, 144.2, 158.5, 168.0, 168.4; ES-MS¯
m/z calcd for C16H11O5 283.0606 [M − H]¯, found 283.0600.
3-Oxo-1,3-dihydroisobenzofuran-1-carboxylic Acid (13-LA). Yield
119 mg (50%); colorless solid. Rf (50% EtOAc/pet. ether): 0.5; mp
1
1735; H NMR (400 MHz, DMSO-d6) δ 2.76−2.82 (m, 1H), 3.44−
3.48 (m, 1H), 6.32−6.34 (m, 1H), 7.74−7.80 (m, 3H), 8.12−8.19 (m,
3H); 13C NMR (125 MHz, DMSO-d6) δ 39.4, 77.8, 120.4, 123.8,
125.1, 126.7, 128.5, 129.7, 129.8, 131.1, 136.3, 149.2, 170.6, 171.1; EI-
MS¯ m/z calcd for C14H9O4 241.0500 [M − H]¯, found 241.0508.
1,4-Phenanthroquinone (22-Q).4d Yield 29 mg (27%); yellow
1
solid. Rf (5% EtOAc/pet. ether): 0.3; H NMR (400 MHz, CDCl3) δ
6.94−7.00 (m, 2H), 7.65 (dt, J1 = 7.8 Hz, J2 = 1.4 Hz, 1H), 7.75 (dt, J1
= 7.3 Hz, J2 = 1.3 Hz, 1H), 7.91 (d, J = 8.3 Hz, 1H), 8.16−8.20 (m,
2H), 9.55 (d, J = 8.7 Hz, 1H).
1
137−140 °C; IR (KBr) cm−1 3200−2600 (br), 2924, 1768; H NMR
(400 MHz, CD3OD) δ 6.06 (s, 1H), 7.63−7.66 (m, 1H), 7.76−7.81
(m, 2H), 7.89 (d, J = 7.56 Hz, 1H); 13C NMR (125 MHz, CD3OD) δ
78.1, 123.1, 124.9, 125.4, 130.2, 134.9, 145.5, 168.9, 170.7; EI-MS+ m/
z calcd for C9H7O4 179.0344 [M + H]+, found 179.0344.
2-(1-Oxo-1,3-dihydronaphtho[2,1-c]furan-3-yl)acetic Acid (24-
LA). Yield 153 mg (82%); colorless solid. Rf (10% MeOH/EtOAc):
0.3; mp 142−145 °C; IR (KBr) cm−1 3000−2600 (br), 2921, 1733,
1
1706; H NMR (400 MHz, DMSO-d6) δ 2.74−2.81 (m, 1H), 3.24−
2,3-Dihydroxy-1,4-naphthoquinone (13-Q). Yield 35 mg (15%);
3.29 (m, 1H), 5.96−5.98 (m, 1H), 7.69 (t, J = 7.8 Hz, 1H), 7.79−7.81
(m, 2H), 8.13 (d, J = 8.2 Hz, 1H), 8.33 (d, J = 8.2 Hz, 1H), 8.80 (d, J
= 8.2 Hz, 1H); 13C NMR (125 MHz, DMSO-d6) δ 38.8, 77.5, 119.7,
120.1, 122.8, 127.8, 128.8, 129.4, 129.6, 133.5, 136.0, 152.0, 170.5,
171.5; EI-MS¯ m/z calcd for C14H9O4 241.0500 [M − H]¯, found
241.0506.
red solid. Rf (EtOAc): 0.4; mp 146−148 °C; IR (KBr) cm−1 3339,
1
1674, 1632, 1590. H NMR (400 MHz, DMSO-d6) δ 7.74−7.76 (m,
2H), 7.90−7.91 (m, 2H); 13C NMR (100 MHz, DMSO-d6) δ 125.8,
130.5, 134.1, 141.1, 181.3; ES-MS¯ m/z calcd for C10H5O4 189.0187
[M − H]¯, found 189.0194.
1,4-Naphthoquinone (14-Q).7b Yield 68 mg (31%); yellow solid. Rf
2-(8-Hydroxy-1-oxo-1,3-dihydronaphtho[2,1-c]furan-3-yl)acetic
Acid (28-LA). Yield 62 mg (52%); colorless solid. mp 218−220 °C; Rf
(15% MeOH/EtOAc) 0.32; IR (KBr) cm−1 3500−2600 (br), 2923,
1
(5% EtOAc/pet. ether): 0.5; H NMR (CDCl3, 400 MHz) δ 6.98 (s,
2H), 7.75−7.78 (m, 2H), 8.0−8.01 (m, 2H).
1
1738, 1702; H NMR (400 MHz, DMSO-d6) δ 2.68−2.74 (m, 1H),
β-Bromo-2-carboxycinnamic Acid (15-CA). Yield 69 mg (62%);
colorless solid. Rf (20% MeOH/EtOAc): 0.3; mp 137−140 °C; IR
(KBr) cm−1 3100−2600 (br), 1812, 1693, 1641; 1H NMR (DMSO-d6,
400 MHz) δ 6.18 (s, 1H), 7.83 (t, J = 7.5 Hz, 1H), 7.97 (t, J = 7.78 Hz,
1H), 8.01 (d, J = 7.76 Hz, 1H), 8.90 (d, J = 8.2 Hz, 1H); 13C NMR
(DMSO-d6, 125 MHz) δ 103.5, 125.8, 126.5, 127.9, 133.4, 135.9,
136.1, 157.2, 165.8, 166.8.
3.18−3.22 (m, 1H), 5.87−5.89 (m, 1H), 7.21 (m, 1H), 7.52 (d, J = 8.2
Hz, 1H), 7.97 (d, J = 8.7 Hz, 1H), 8.11 (d, J = 2.3 Hz, 1H), 8.18 (d, J
= 8.2 Hz, 1H); 13C NMR (125 MHz, DMSO-d6) δ 39.1, 77.2, 104.9,
116.4, 117.9, 120.0, 128.1, 130.9, 131.2, 135.8, 152.3, 158.8, 170.8,
171.5; EI-MS¯ m/z calcd for C14H9O5 257.0450 [M − H]¯, found
257.0455.
1,6-Diketopyrene (29-Q1). Yield 64 mg (60%); yellow solid. Rf
(25% EtOAc/pet. ether): 0.5; mp 250−253 °C; IR (KBr) cm−1 3000,
2921, 2851, 1636; 1H NMR (400 MHz, CDCl3) δ 6.71 (d, J = 9.8 Hz,
2H), 7.68 (d, J = 9.8 Hz, 2H), 7.84 (d, J = 7.7 Hz, 2H), 8.49 (d, J = 7.7
Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 127.22, 129.9, 130.2, 130.6,
130.7, 133.7, 141.1, 185.4; EI-MS¯ m/z calcd for C16H8O2 232.0524
[M]¯, found 232.0523.
β-Phenyl-2-carboxycinnamic Acid (16-CA). Yield 87 mg (72%);
colorless solid. Rf (20% MeOH/EtOAc): 0.4; mp 146−148 °C; IR
1
(KBr) cm−1 3000−2700 (br), 1683, 1613; H NMR (DMSO-d6, 400
MHz) δ 6.36 (s, 1H), 7.13 (d, J = 7.36 Hz, 1H), 7.21−7.24 (m, 2H),
7.30−7.33 (m, 3H), 7.47 (dt, J1 = 7.6 Hz, J2 = 1.2 Hz, 1H), 7.57 (dt, J1
= 7.4 Hz, J2 = 1.2 Hz, 1H), 7.93 (d, J = 7.8 Hz, 1H); 13C NMR
(DMSO-d6, 125 MHz) δ 117.3, 125.8, 127.7, 128.1, 128.8, 129.4,
130.5, 132.1, 133.6, 140.3, 141.0, 155.9, 166.9, 167.6; ESI-MS¯ m/z
calcd for C16H11O4 267.0657 [M − H]¯, found 267.0652.
1,8-Diketopyrene (29-Q2). Yield 30 mg (29%); red solid. Rf (25%
EtOAc/pet. ether): 0.45; mp 250−255 °C; IR (KBr) cm−1 3000, 2921,
E
J. Org. Chem. XXXX, XXX, XXX−XXX