The Journal of Organic Chemistry
Article
MHz, DMSO-d ) δ 13.08 (br s, 1H), 7.91 (dd, J = 1.9 Hz, J = 0.9
NMR (400 MHz, DMSO-d ) δ 13.02 (br s, 1H), 8.00 (d, J = 8.7 Hz,
2H), 7.26 (d, J = 8.7 Hz, 2H), 2.29 (s, 3H).
6
1
2
6
Hz, 1H), 7.21 (dd, J = 3.5 Hz, J = 0.9 Hz, 1H), 6.65 (dd, J = 3.5
1
2
1
Hz, J = 1.8 Hz, 1H).
3-Acetoxybenzoic Acid (10b). From methyl 3-acetoxybenzoate
(9b, 0.893 g, 4.6 mmol); white solid; yield: 0.789 g (95%); mp 127−
2
Indole-3-carboxylic Acid (4y). From methyl indole-3-carboxylate
3y, 0.438 g, 2.5 mmol); light yellow solid; yield: 0.390 g (96%);
31
1
(
129 °C (lit.: 131−134 °C); R = 0.15 (PE/EA = 3:1). H NMR
f
3
1
decomposed at above 213 °C (lit.: 232−234 °C dec.); R = 0.67
(400 MHz, DMSO-d ) δ 13.22 (br s, 1H), 7.84 (dt, J = 7.8 Hz, J =
f
6
1
2
1
(
PE/EA = 3:1). H NMR (400 MHz, DMSO-d ) δ 11.93 (br s, 1H),
1.3 Hz, 1H), 7.67 (dd, J = 2.4 Hz, J = 1.5 Hz, 1H), 7.56 (t, J = 7.9
6
1 2
1
1.82 (s, 1H), 8.10−7.92 (m, 2H), 7.53−7.38 (m, 1H), 7.21−7.17
Hz, 1H), 7.40 (ddd, J = 8.1 Hz, J = 2.4 Hz, J = 1.1 Hz, 1H), 2.30 (s,
1 2 3
1
3
1
(
m, 1H), 7.17−7.13 (m, 1H). C{ H} NMR (101 MHz, DMSO-d )
3H).
6
δ 166.4, 136.9, 132.7, 126.5, 122.6, 121.4, 121.0, 112.7, 107.8.
H-Indazole-4-carboxylic Acid (4z). From methyl 1H-indazole-4-
carboxylate (3z, 0.440 g, 2.5 mmol); off-white solid; yield: 0.400 g
4-(Benzoyloxy)benzoic Acid (10c). From methyl 4-(benzoyloxy)-
1
benzoate (9c, 0.176 g, 0.69 mmol); white solid; yield: 0.165 g (99%);
1
8
1
mp 224−226 °C (lit.: 220−222 °C); R = 0.75 (PE/EA = 1:1). H
f
1
(
98%); R = 0.61 (EA). H NMR (400 MHz, DMSO-d ) δ 13.29 (br
f
6
NMR (400 MHz, DMSO-d ) δ 13.08 (br s, 1H), 8.16 (dd, J = 8.4
6
1
s, 2H), 8.40 (d, J = 1.0 Hz, 1H), 7.82 (dd, J = 12.1 Hz, J = 7.8 Hz,
1
2
Hz, J = 1.3 Hz, 2H), 8.06 (d, J = 8.8 Hz, 2H), 7.78 (tt, J = 7.6 Hz, J
2
1
2
1
3
1
2
H), 7.47 (dd, J = 8.3 Hz, J = 7.2 Hz, 1H). C{ H} NMR (101
1 2
= 1.2 Hz, 1H), 7.63 (t, J = 7.6 Hz, 2H), 7.44 (d, J = 8.8 Hz, 2H).
MHz, DMSO-d ) δ 167.8, 140.9, 134.2, 125.9, 124.2, 123.4, 121.7,
13
1
6
C{ H} NMR (101 MHz, DMSO-d ) δ 167.1, 164.7, 154.5, 134.7,
6
1
15.8.
1
31.4, 130.4, 129.5, 129.1, 129.1, 122.7.
3
-Phenylpropanoic Acid (4aa). White solid; yield: 0.746 g (99%);
4
-(Pivaloyloxy)benzoic Acid (10d). From methyl 4-(pivaloyloxy)-
31
1
mp 47−49 °C (lit.: 45−48 °C); R = 0.40 (PE/EA = 3:1). H NMR
f
benzoate (9d, 0.520 g, 2.2 mmol); white crystalline solid; yield: 0.482
(
=
400 MHz, CDCl ) δ 10.26 (br s, 1H), 7.37−7.26 (m, 2H), 7.22 (t, J
1
3
g (98%); mp 187−189 °C; R = 0.18 (PE/EA = 3:1). H NMR (400
f
6.3 Hz, 3H), 2.96 (t, J = 7.8 Hz, 2H), 2.68 (t, J = 7.8 Hz, 2H).
Adamantane-1-carboxylic Acid (4ab). From methyl adamantane-
MHz, DMSO-d ) δ 13.04 (br s, 1H), 8.00 (d, J = 8.6 Hz, 2H), 7.24
6
(
d, J = 8.7 Hz, 2H), 1.31 (s, 9H).
-(Tosyloxy)benzoic Acid (10e). From methyl 4-(tosyloxy)-
benzoate (9e, 0.476 g, 1.55 mmol); off-white solid; yield: 0.448 g
1-carboxylate (3ab, 0.409 g, 2.1 mmol) using iodine (0.799 g, 3.15
4
mmol, 1.5 equiv) and excess aluminum; white solid; yield: 0.359 g
31
(
94%); mp 172−174 °C (lit.: 172−174 °C); R = 0.50 (PE/EA =
37
f
(
98%); mp 170−172 °C (lit.: 170−171.5 °C); R = 0.07 (PE/EA =
1
f
1
0:1). H NMR (400 MHz, DMSO-d ) δ 11.97 (br s, 1H), 1.97−1.91
1
6
3
7
2
:1). H NMR (400 MHz, DMSO-d ) δ 7.94 (d, J = 8.7 Hz, 2H),
1
3
1
6
(
m, 3H), 1.78 (d, J = 3.0 Hz, 6H), 1.72−1.56 (m, 6H). C{ H}
.76 (d, J = 8.4 Hz, 2H), 7.48 (d, J = 8.2 Hz, 2H), 7.16 (d, J = 8.7 Hz,
H), 2.42 (s, 3H).
NMR (101 MHz, DMSO-d ) δ 178.9, 40.0, 39.0, 36.5, 27.9.
6
Lauric Acid (4ac). White solid; yield: 0.979 g (97%); mp 44−46
31
1
2-(Tosyloxy)benzoic Acid (10f). From methyl 2-(tosyloxy)-
°
C (lit.: 44−46 °C); R = 0.41 (PE/EA = 3:1). H NMR (400 MHz,
f
benzoate (9f, 0.306 g, 1 mmol); white solid; yield: 0.282 g (96%);
CDCl ) δ 2.35 (t, J = 7.5 Hz, 2H), 1.63 (p, J = 7.5 Hz, 2H), 1.43−
38
1
3
mp 165−167 °C (lit.: 165−171 °C); R = 0.21 (PE/EA = 1:1). H
f
1
.14 (m, 18H), 0.88 (t, J = 6.8 Hz, 3H).
NMR (400 MHz, DMSO-d ) δ 13.16 (br s, 1H), 7.81 (dd, J = 7.7
6
1
2
-Cyanobenzoic Acid (6a). From ethyl 2-cyanobenzoate (5b); off-
3
1
2
= 1.8 Hz, 1H), 7.70 (d, J = 8.4 Hz, 2H), 7.57 (ddd, J
1
= 8.2 Hz,
white solid; yield: 0.731 g (99%); mp 211−213 °C (lit.: 212 °C); Rf
1
= 1.8 Hz, 1H), 7.46 (d, 8.4 Hz, 2H), 7.42 (dt, J = 7.6
3 1
=
0.03 (PE/EA = 3:1). H NMR (400 MHz, DMSO-d ) δ 13.88 (br s,
6
Hz, J = 1.2 Hz, 1H), 7.01 (dd, J = 8.2 Hz, J = 1.1 Hz, 1H), 2.43 (s,
2
1
2
1H), 8.16−8.08 (m, 1H), 8.03−7.95 (m, 1H), 7.88−7.76 (m, 2H).
1
3
1
3
H). C{ H} NMR (101 MHz, DMSO-d ) δ 165.9, 147.4, 146.2,
6
Phthalic Acid (6b). From ethyl phthalate (5c); white solid; yield:
30
133.8, 132.1, 132.1, 130.6, 128.7, 128.0, 127.0, 123.9, 21.7.
0
.799 g (97%); mp 198−200 °C (lit.: 208−209 °C); R = 0.05
f
1
4-(Phenoxycarbonyl)benzoic Acid (10g). From methyl 4-
(EA). H NMR (400 MHz, DMSO-d ) δ 13.10 (br s, 2H), 7.70−7.65
(m, 2H), 7.63−7.53 (m, 2H).
6
(
phenoxycarbonyl)benzoate (9g, 0.686 g, 2.68 mmol); white solid;
39
yield: 0.648 g (99%); mp 227−229 °C (lit.: 230−235 °C); R = 0.58
f
5
-Methyl-2H-pyrazole-3-carboxylic Acid (6c). From ethyl 5-
1
(
PE/EA = 1:1). H NMR (400 MHz, DMSO-d ) δ 13.47 (br s, 1H),
6
methylpyrazole-3-carboxylate (5d, 0.385 g, 2.5 mmol) using
substoichiometric amount of iodine (0.476 g, 1.875 mmol, 0.75
8
.25 (d, J = 8.6 Hz, 2H), 8.15 (d, J = 8.6 Hz, 2H), 7.56−7.44 (m,
1
3
1
3
4
2H), 7.39−7.27 (m, 3H). C{ H} NMR (101 MHz, DMSO-d ) δ
167.0, 164.5, 151.0, 135.9, 133.0, 130.5, 130.2, 130.1, 126.6, 122.3.
6
equiv); off-white solid; yield: 0.295 g (93%); mp 236−238 °C (lit.:
1
2
1
35−237 °C); R = 0.03 (EA). H NMR (400 MHz, DMSO-d ) δ
f
6
p-Anisic Acid (10h). White solid; yield: 0.691 g (90%); mp 183−
2.91 (br s, 2H), 6.45 (s, 1H), 2.23 (s, 3H).
31
1
1
(
85 °C (lit.: 182−185 °C); R = 0.24 (PE/EA = 3:1). H NMR
Benzylmalonic Acid (6d). From diethyl benzylmalonate (5e, 0.626
g, 2.5 mmol) and iodine (0.951 g, 3.75 mmol, 1.5 equiv); light yellow
f
400 MHz, DMSO-d ) δ 11.83 (br s, 1H), 7.91 (d, J = 8.4 Hz, 2H),
6
3
1
7.00 (d, J = 8.4 Hz, 2H), 3.82 (s, 3H).
solid; yield: 0.450 g (93%); mp 115−117 °C (lit.: 117−120 °C); R
f
1
p-Ethoxybenzoic Acid (10i). White solid; yield: 0.802 g (89%); mp
=
0.10 (PE/EA = 1:1). H NMR (400 MHz, DMSO-d ) δ 12.76 (br s,
6
3
1
1
1
3
1
197−198 °C (lit.: 197−199 °C); R = 0.29 (PE/EA = 3:1). H NMR
2
H), 7.31−7.16 (m, 5H), 3.56 (t, C{ H} NMR (101 MHz, DMSO-
f
(
400 MHz, DMSO-d ) δ 12.61 (br s, 1H), 7.88 (d, J = 8.9 Hz, 2H),
d ) δ 170.8, 139.0, 129.2, 128.7, 126.8, 53.8, 34.6.
6
6
7.00 (d, J = 8.9 Hz, 2H), 4.10 (q, J = 7.0 Hz, 2H), 1.34 (t, J = 7.0 Hz,
5
-Iodopentanoic Acid (8a). Yellow solid; yield: 1.097 g (96%); mp
35
1
3
H).
5
9.5−61.5 °C (lit. 58 °C); R = 0.77 (PE/EA = 1:1). H NMR (400
MHz, DMSO-d ) δ 12.06 (br s, 1H), 3.27 (t, J = 6.8 Hz, 2H), 2.24 (t,
f
4
-Isopropoxybenzoic Acid (10j). White solid; yield: 0.410 g
6
31
(90%); mp 163−165 °C (lit.: 164−167 °C); R = 0.32 (PE/EA =
J = 7.4 Hz, 2H), 1.77 (qui, J = 7.0 Hz, 2H), 1.57 (qui, J = 7.6 Hz,
f
1
3
8
:1). H NMR (400 MHz, DMSO-d ) δ 12.59 (br s, 1H), 7.87 (d, J =
.8 Hz, 2H), 6.98 (d, J = 8.7 Hz, 2H), 4.71 (hept, J = 5.8 Hz, 1H),
2
H).
-Iodohexanoic Acid (8b). Yellow solid; yield: 1.203 g (99%); mp
8−50 °C (lit.: 41 °C); R = 0.77 (PE/EA = 1:1). H NMR (400
6
6
35
1
4
1.29 (d, J = 6.0 Hz, 6H).
f
MHz, CDCl ) δ 10.47 (br s, 1H), 3.19 (t, J = 7.0 Hz, 2H), 2.38 (t, J =
2-(4-(4-Chlorobenzoyl)phenoxy)-2-methylpropanoic Acid (10k).
From fenofibrate (9k, 0.722 g, 2 mmol); white solid; yield: 0.622 g
3
7
1
3
.5 Hz, 2H), 1.85 (qui, J = 7.0 Hz, 2H), 1.66 (qui, J = 7.5 Hz, 2H),
.50−1.42 (m, 2H). C{ H} NMR (101 MHz, CDCl ) δ 180.1, 33.9,
3.1, 29.9, 23.6, 6.5.
40
1
3
1
(97%); mp 180−182 °C (lit.: 179−180 °C); R
= 0.43 (PE/EA =
1:1). H NMR (400 MHz, DMSO-d ) δ 13.17 (br s, 1H), 7.72 (d, J =
6
3
f
1
1
5-Iodopentadecanoic Acid (8c). Yellow solid; yield: 1.841 g
8.9 Hz, 2H), 7.71 (d, J = 8.6 Hz, 2H), 7.62 (d, J = 8.6 Hz, 2H), 6.93
(d, J = 8.9 Hz, 2H), 1.60 (s, 6H).
4-Acetoxysalicylic Acid (12a). From methyl 2,4-diacetoxybenzoate
36
1
(
99%); mp 76−78 °C (lit.: 78 °C); R = 0.78 (PE/EA = 3:1). H
NMR (400 MHz, DMSO-d ) δ 11.95 (br s, 1H), 3.26 (t, J = 6.9 Hz,
f
6
2
=
H), 2.18 (t, J = 7.4 Hz, 2H), 1.74 (qui, J = 6.9 Hz, 2H), 1.48 (qui, J
7.0 Hz, 2H), 1.39−1.15 (m, 20H).
-Acetoxybenzoic Acid (10a). White solid; yield: 0.892 g (99%);
(11b, 0.767 g, 3.04 mmol); yellow solid; yield: 0.591 g (99%); mp
4
1
1
147−149 °C (lit.: 150 °C); R = 0.1 (PE/EA = 3:1). H NMR (400
f
4
MHz, DMSO-d ) δ 7.82 (d, J = 8.6 Hz, 1H), 6.75 (d, J = 2.2 Hz, 1H),
6
31
1
mp 192−193 °C (lit.: 190−194 °C); R = 0.55 (PE/EA = 1:1). H
6.70 (dd, J = 8.6 Hz, J = 2.3 Hz, 1H), 2.27 (s, 3H).
f
1
2
4
259
J. Org. Chem. 2021, 86, 4254−4261