Hydrolysis of Diazonium Salts Using a Two-Phase System (CPME and Water) 415
then extracted with AcOEt and dried over MgSO4.
After purification by silica gel column chromatogra-
phy, phenol 3 was obtained.
J = 8.1, 2.3, 0.9 Hz, 1H), 7.12 (t, J = 7.9 Hz, 1H).
13
C NMR (CDCl3) δ (ppm): 55.4, 101.7, 106.6, 108.0,
+
130.3, 156.8, 160.9. MS (EI) m/z (%): 124 (M , 100),
94 (61), 81 (33), 66 (33), 53 (62), 41 (18).
3
-(4-Nitrophenoxy)phenol (3a). Yield 1.110 g
1
(
(
1
96%), mp 95–96°C (Lit. [18] 96–97°C). H NMR
CDCl3) δ (ppm): 5.26 (s, 1H, OH), 6.59 (t, J = 2.4 Hz,
3-Acetylphenol (3g). Yield 0.629 g (92%), mp
1
95–96°C (Lit. [24] 96°C). H NMR (CDCl3) δ (ppm):
2.61 (s, 3H, CH3), 6.85 (s, 1H, OH), 7.12 (ddd, J = 8.0,
2.7, 0.9 Hz, 1H), 7.34 (t, J = 8.0 Hz, 1H), 7.51 (dt, J =
H), 6.65 (ddd, J = 8.2, 2.4, 0.8 Hz, 1H), 6.72 (ddd, J
=
8.2, 2.4, 0.8 Hz, 1H), 7.04 (dt, J = 9.2, 2.1 Hz, 2H),
1
3
7
.27 (t, J = 8.2 Hz, 1H), 8.20 (dt, J = 9.2, 2.1 Hz, 2H).
8.0, 0.9 Hz, 1H), 7.55–7.56 (m, 1H). C NMR (CDCl3)
1
3
C NMR (CDCl3) δ (ppm): 108.0, 112.6, 112.7, 117.4,
δ (ppm): 26.9, 114.8, 121.0, 121.2, 130.0, 138.4, 156.5,
+
1
26.1, 131.1, 142.7, 155.9, 157.4, 163.2. MS (EI) m/z
199.5. MS (EI) m/z (%): 136 (M , 62), 121 (91), 93
(65), 65 (49), 43 (100).
+
(
%): 231 (M , 100), 207 (24), 128 (52), 65 (82).
3
-Phenoxyphenol (3b). Yield 0.882 g (95%), oil
3-Nitrophenol (3h). Yield 0.519 g (75%), mp 95–
96°C (Lit. [7] 95–96°C). H NMR (CDCl3) δ (ppm):
1
1
(
Lit. [19]). H NMR (CDCl3) δ (ppm): 4.84 (s, 1H,
OH), 6.48 (t, J = 2.4 Hz, 1H), 6.56 (dd, J = 8.2,
5.39 (s, 1H, OH), 7.18 (ddd, J = 8.2, 2.3, 0.9 Hz, 1H),
2
7
8
.4, 1H), 6.58 (dd, J = 8.2, 2.4 Hz, 1H), 7.03 (d, J =
7.41 (t, J = 8.2 Hz, 1H), 7.70 (t, J = 2.3 Hz, 1H), 7.82
1
3
.3 Hz, 2H), 7.12 (t, J = 7.3 Hz, 1H), 7.17 (t, J =
(ddd, J = 8.2, 2.3, 0.9 Hz, 1H). C NMR (CDCl3)
1
3
.2 Hz, 1H), 7.34 (t, J = 7.3 Hz, 2H). C NMR
δ (ppm): 110.6, 116.0, 122.1, 130.4, 149.2, 156.3. MS
+
(
CDCl3) δ (ppm): 106.0, 110.2, 111.1, 119.4, 123.7,
(EI) m/z (%): 139 (M , 70), 93 (42), 81 (24), 65 (100),
1
29.9, 130.5, 156.8, 156.9, 158.8. MS (EI) m/z (%):
53 (40).
+
186 (M , 100), 157 (21), 129 (27), 77 (35), 51 (94).
3
-Trifluoromethylphenol (3i). Yield 0.760 g
1
3
-Benzyloxyphenol (3c). Yield 0.643 g (64%),
(94%), oil (Lit. [25]). H NMR (CDCl3) δ (ppm): 5.04
(s, 1H, OH), 7.01 (dd, J = 2.3, 8.2 Hz, 1H), 7.08
(s, 1H), 7.20 (dd, J = 8.2, 2.3 Hz, 1H), 7.36 (t, J =
1
mp 49–50°C (Lit. [20] 50–51°C). H NMR (CDCl3)
δ (ppm): 4.71 (s, 1H, OH), 5.04 (s, 2H, CH2), 6.44
1
3
(
ddd, J = 8.2, 2.4, 0.9, 1H), 6.48 (t, J = 2.4 Hz, 1H),
8.2 Hz, 1H). C NMR (CDCl3) δ (ppm): 112.5 (q, J
= 3.7 Hz), 117.8, (q, J = 3.7 Hz), 119.0, 124.0 (q, J =
274 Hz), 130.4, 132.3 (q, J = 33 Hz), 155.8. MS (EI)
6
1
7
1
9
.57 (ddd, J = 8.2, 2.4, 0.9 Hz, 1H), 7.14 (t, J = 8.2 Hz,
H), 7.33–7.44 (m, 5H). 13C NMR (CDCl3) δ (ppm):
0.1, 102.6, 107.5, 108.2, 127.6, 128.1, 128.7, 130.3,
+
m/z (%): 162 (M , 100), 143 (33), 112 (24), 63 (18).
+
36.9, 156.7, 160.2. MS (EI) m/z (%): 200 (M , 11),
1 (100), 65 (15), 51 (6).
3-Hydroxybenzoic acid (3j). Yield 0.678
98%), mp 197–198°C (Lit. [26] 199–200°C).
g
H
1
(
3
-Isopropylphenol (3d). Yield 0.652 g (96%), oil
NMR (DMSO-d6) δ (ppm): 7.01 (ddd, J = 7.9, 2.4, 1.2
Hz, 1H), 7.31 (t, J = 7.9 Hz, 1H), 7.35 (t, J = 2.4 Hz,
1H), 7.40 (d, J = 7.9 Hz, 1H), 9.77 (s, 1H, OH), 12.8
1
(
Lit. [21]). H NMR (CDCl3) δ (ppm): 1.23 (d, J = 6.9
Hz, 6H, CH3), 2.86 (sep, J = 6.9 Hz, 1H, CH), 4.76
1
3
(
(
s, 1H, OH), 6.65 (ddd, J = 7.7, 2.2, 0.9 Hz, 1H), 6.71
t, J = 2.2 Hz, 1H), 6.81 (d, J = 7.7 Hz, 1H), 7.16 (t,
(brs, 1H, COOH). C NMR (DMSO-d6) δ (ppm):
116.3, 120.4, 120.5, 130.1, 132.5, 157.9, 167.8. MS
1
3
−
J = 7.7 Hz, 1H). C NMR (CDCl3) δ (ppm): 24.0,
(Neg-DART) m/z: 137 ([M – H] ).
3
(
(
4.1, 112.7, 113.4, 119.1, 129.5, 151.1, 155.6. MS
+
EI) m/z (%): 136 (M , 38), 121 (100), 103 (15), 91
23), 77 (24), 65 (11), 51 (15), 41 (21).
o-Cresol (3k). Yield 0.449 g (83%), oil (Lit. [22]).
1
H NMR (CDCl ) δ (ppm): 2.25 (s, 3H, CH ), 4.72 (s,
3
3
1
H, OH), 6.76 (d, J = 7.7 Hz, 1H), 6.85 (td, J = 7.7,
13
m-Cresol (3e). Yield 0.504 g (93%), oil (Lit.
1.2 Hz, 1H), 7.06–7.13 (m, 2H). C NMR (CDCl3) δ
1
[
4
8
22]). H NMR (CDCl3) δ (ppm): 2.30 (s, 3H, CH3),
(ppm): 15.9, 115.0, 120.9, 123.9, 127.3, 131.2, 153.8.
MS (EI) m/z (%): 108 (M , 100), 107 (83), 90 (25), 79
(42), 51 (45), 40 (12).
+
.78 (s, 1H, OH), 6.62–6.66 (m, 2H), 6.75 (d, J =
1
3
.0 Hz, 1H), 7.12 (t, J = 8.0 Hz, 1H). C NMR (CDCl3)
δ (ppm): 21.4, 112.4, 116.2, 121.8, 129.6, 140.0, 155.4.
+
MS (EI) m/z (%): 108 (M , 100), 107 (97), 90 (17), 79
41), 51 (35), 40 (21).
Salicylic acid (3l). Yield 0.614 g (89%), mp
1
(
157.5–158.5°C (Lit. [27] 157.5–158°C). H NMR
(
DMSO-d6) δ (ppm): 6.92 (t, J = 7.2 Hz, 1H), 6.95
3
-Methoxyphenol (3f). Yield 0.565g (91%), oil
(d, J = 7.2 Hz, 1H), 7.51 (td, J = 7.6, 0.6 Hz, 1H),
1
13
(
Lit. [23]). H NMR (CDCl3) δ (ppm): 3.77 (s, 3H,
7.79 (dd, J = 7.6, 1.6 Hz, 1H), 11.50 (brs, 1H).
C
CH3), 5.15 (s, 1H, OH), 6.41–6.44 (m, 2H), 6.50 (ddd,
NMR (DMSO-d6) δ (ppm): 113.5, 117.6, 119.7, 130.8,
Heteroatom Chemistry DOI 10.1002/hc