The Journal of Organic Chemistry
Page 18 of 34
1
2
3
4
5
2H), 6.84 (brs, 1H), 6.68 (bs, 2H), 2.57 (s, 3H), 2.31 (brs, 6H). – 13C NMR (75 MHz, CDCl3): δ
= 196.7, 162.2, 155.3, 139.9, 131.6, 130.5, 126.3, 117.7, 117.2, 26.4, 21.2. – LRMS (DCI,
positive mode) m/z (rel intensity) 241 ([MH]+, 100), 258 ([MNH4]+, 25).
6
7
8
9
4-(3,5-Dimethylphenoxy)benzaldehyde (1f). Using the general procedure with DMF as
solvent, from 3,5-dimethylphenol and either 4-iodobenzaldehyde or 4-bromobenzaldehyde,
the expected diaryl ether 1f was isolated as a yellow solid. – Yields 39% (44 mg from the
iodo derivative) and 60% (68 mg from the bromo derivative). – Rf = 0.50 (90:10
cyclohexane/EtOAc). – M.p. 45-47 °C. – FTIR-ATR (neat) 2910, 2820, 2740, 1702, 1580,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
1500, 1292, 1230, 1161 cm-1. – H NMR (300 MHz, CDCl3): δ = 9.92 (s, 1H), 7.86-7.81 (m,
2H), 7.07-7.02 (m, 2H), 6.86 (brs, 1H), 6.70 (brs, 2H), 2.32 (brs, 6H). – 13C NMR (75 MHz,
CDCl3): δ = 190.7, 163.4, 154.9, 140.0, 131.9, 131.0, 126.6, 118.0, 117.5, 21.2. – HRMS
(DCI, positive mode): m/z: calcd for C15H15O2 227.1072, found 227.1070 [MH]+.
2-(3,5-Dimethylphenoxy)benzaldehyde (1g).31b Using the general procedure with
toluene as solvent, from 3,5-dimethylphenol and 2-bromobenzaldehyde, the expected diaryl
ether 1g was isolated as an yellow oil. – Yield 19% (22 mg). – Rf = 0.60 (90:10
cyclohexane/EtOAc). – FTIR-ATR (neat) 3010, 2920, 2850, 1690, 1600, 1480, 1460, 1300,
1230 cm-1. – 1H NMR (300 MHz, CDCl3): δ = 10.51 (d, 4J = 0.8 Hz, 1H), 7.93 (dd, 3J = 7.8 Hz,
4J = 1.8 Hz, 1H), 7.51 (ddd, 3J = 8.4 Hz, 3J = 7.3 Hz, 4J = 1.8 Hz, 1H), 7.17 (brt, 3J = 7.6 Hz,
3
4
1H), 6.90 (dd, J = 8.4 Hz, J = 0.8 Hz, 1H), 6.82 (brs, 1H), 6.68 (brs, 2H), 2.31 (brs, 6H). –
13C NMR (75 MHz, CDCl3): δ = 189.5, 160.2, 156.3, 140.0, 135.7, 128.2, 126.8, 126.0, 123.1,
118.5, 117.0, 21.3. – LRMS (DCI, positive mode) m/z (rel intensity) 226 ([M]+, 10), 227
([MH]+, 100), 244 ([MNH4]+, 40).
Isopropyl 4-(3,5-dimethylphenoxy)benzoate (1h). Using the general procedure with
toluene as solvent, from 3,5-dimethylphenol and isopropyl 4-iodobenzoate, the expected
diaryl ether 1h was isolated as an orange oil. – Yield 70% (100 mg). – Rf = 0.80 (90:10
cyclohexane/EtOAc). – FTIR-ATR (neat) 2979, 2916, 1713, 1590, 1503, 1274, 1235, 1161,
1098 cm-1. – 1H NMR (300 MHz, CDCl3): δ = 8.02-7.97 (m, 2H), 6.99-6.95 (m, 2H), 6.81 (brs,
3
3
1H), 6.67 (brs, 2H), 5.23 (sept, J = 6.3 Hz, 1H), 2.30 (brs, 6H), 1.36 (d, J = 6.3 Hz, 6H). –
13C NMR (75 MHz, CDCl3): δ = 165.6, 161.7, 155.7, 139.8, 131.5, 126.0, 125.0, 117.5, 117.3,
68.1, 22.0, 21.2. – HRMS (DCI, positive mode): m/z: calcd for C18H21O3 285.1491, found
285.1479 [MH]+.
Methyl 4-(3,5-dimethylphenoxy)benzoate (1i).12a Using the general procedure with
toluene as solvent, from 3,5-dimethylphenol and methyl 4-iodobenzoate, the expected diaryl
ether 1i was isolated as an orange oil. – Yield 41% (53 mg). – Rf = 0.50 (90:10
cyclohexane/EtOAc). – FTIR-ATR (neat) 2949, 2919, 2846, 1721, 1590, 1505, 1435, 1278,
1
1235, 1163, 1112 cm-1. – H NMR (300 MHz, CDCl3): δ = 8.02-7.97 (m, 2H), 6.99-6.94 (m,
2H), 6.83 (brs, 1H), 6.68 (brs, 2H), 3.90 (s, 3H), 2.31 (s, 6H). – 13C NMR (75 MHz, CDCl3): δ
= 166.6, 162.0, 155.5, 139.9, 131.6, 126.2, 124.2, 117.7, 117.2, 51.9, 21.3. – LRMS (APCI,
positive mode) m/z (rel intensity) 257 ([MH]+, 100).
4-(3,5-Dimethylphenoxy)benzoic acid (1j).31c Using the general procedure with toluene
as solvent at 140°C, from 3,5-dimethylphenol and 4-iodobenzoic acid, the expected diaryl
ether 1j was isolated as a brown oil. – Yield 80% (97 mg). – Rf = 0.50 (50:50
cyclohexane/EtOAc). – FTIR-ATR (neat) 2920, 2850, 2560, 1680, 1590, 1510, 1430, 1290,
1
1230, 1160 cm-1. – H NMR (300 MHz, DMSO-d6): δ = 7.94-7.91 (m, 2H), 7.00-6.97 (m, 2H),
ACS Paragon Plus Environment