PAPER
Methyl Salicylate as a Methylation Agent
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1H NMR (400 MHz, CDCl3): δ = 7.87 (d, J = 8.0 Hz, 1 H), 7.30 (d,
J = 7.6 Hz, 1 H), 6.66–6.72 (m, 2 H), 5.71 (br, 2 H), 3.87 (s, 3 H).
1H NMR (400 MHz, CDCl3): δ = 7.27–7.31 (m, 3 H), 7.20 (d, J =
7.6 Hz, 2 H), 3.67 (s, 3 H), 2.97 (t, J = 8.0 Hz, 2 H), 2.66 (t, J =
8.0Hz, 2 H).
Methyl 3-Aminobenzoate (3f)16
Colorless oil; yield: 3.06 g (81%).
1H NMR (400 MHz, CDCl3): δ = 7.44 (d, J = 7.6 Hz, 1 H), 7.36 (s,
1 H), 7.23 (t, J = 8.0 Hz, 1 H), 6.88 (d, J = 8.0 Hz, 1 H), 3.89 (s, 3
H), 3.59 (br, 2 H).
Methyl Naphthalene-1-acetate (3s)7h
Colorless oil; yield: 4.75 g (95%).
1H NMR (400 MHz, CDCl3): δ = 8.00 (d, J = 8.0 Hz, 1 H), 7.87 (d,
J = 7.6 Hz, 1 H), 7.80 (d, J = 7.2 Hz, 1 H), 7.40–7.56 (m, 4 H), 4.08
(s, 2 H), 3.67 (s, 3 H).
Methyl 4-Aminobenzoate (3g)16
White solid; yield: 2.98 g (79%); mp 110–112 °C.
1H NMR (400 MHz, CDCl3): δ = 7.86 (d, J = 8.8 Hz, 2 H), 6.65 (d,
J = 8.8 Hz, 2 H), 4.04 (br, 2 H), 3.85 (s, 3 H).
Methyl Mandelate (3t)23
White solid; yield: 3.07 g (74%); mp 53–54 °C.
1H NMR (400 MHz, CDCl3): δ = 7.32–7.43 (m, 5 H), 5.18 (s, 1 H),
3.76 (s, 3 H), 3.66 (br, 1 H).
Methyl 3-Acetamidobenzoate (3h)7i
Methyl Methacrylate (3u)24
Colorless oil; yield: 1.80 g (72%).
1H NMR (400 MHz, CDCl3): δ = 6.11 (m, 1 H), 5.57 (m, 1 H), 3.76
(s, 3 H), 1.95 (t, J = 1.2 Hz, 3 H).
White solid; yield: 4.15 g (86%); mp 135–136 °C.
1H NMR (400 MHz, CDCl3): δ = 8.02 (s, 1 H), 7.91 (d, J = 8.4 Hz,
1 H), 7.78 (d, J = 7.6 Hz, 1 H), 7.68 (br, 1 H), 7.41 (t, J = 8.0 Hz, 1
H), 3.90 (s, 3 H), 2.21 (s, 3 H).
Methyl 4-Nitrobenzoate (3i)7i
Pale yellow solid; yield: 4.16 g (92%); mp 95–96 °C.
Methyl Cinnamate (3v)7i
Colorless oil; yield: 3.2 g (79%).
1H NMR (400 MHz, CDCl3): δ = 8.31 (d, J = 9.2 Hz, 2 H), 8.23 (d,
J = 8.4 Hz, 2 H), 3.99 (s, 3 H).
1H NMR (400 MHz, CDCl3): δ = 7.72 (d, J = 16.0 Hz, 1 H), 7.52 (s,
2 H), 7.39 (s, 3 H), 6.47 (d, J = 16.0 Hz, 1 H), 3.81 (s, 3 H).
Methyl 3-Nitrobenzoate (3j)7h
Pale yellow solid; yield: 4.21 g (93%); mp 77–78 °C.
Methyl 1H-Indol-3-ylacetate (3w)7i
White solid; yield: 3.73 g (79%); mp 49–50 °C.
1H NMR (400 MHz, CDCl3): δ = 8.88 (s, 1 H), 8.43 (d, J = 8.0 Hz,
1 H), 8.38 (d, J = 8.0 Hz, 1 H), 7.69 (t, J = 8.0 Hz, 1 H), 4.00 (s, 3 H).
1H NMR (400 MHz, CDCl3): δ = 8.08 (br, 1 H), 7.63 (d, J = 7.6 Hz,
1 H), 7.36 (d, J = 8.0 Hz, 1 H), 7.12–7.22 (m, 3 H), 3.79 (s, 2 H),
3.70 (s, 3 H).
Methyl 2-Chlorobenzoate (3k)18
Colorless oil; yield: 3.83 g (90%).
1H NMR (400 MHz, CDCl3): δ = 7.84 (d, J = 7.6 Hz, 1 H), 7.40–
7.47 (m, 2 H), 7.34 (t, J = 7.6 Hz, 1 H), 3.94 (s, 3 H).
Methyl Nicotinate (3x)18
White solid; yield: 2.77 g (81%); mp 38–39 °C.
1H NMR (400 MHz, CDCl3): δ = 9.24 (s, 1 H), 8.80 (d, J = 4.4 Hz,
1 H), 8.34 (d, J = 8.0 Hz, 1 H), 7.43 (dd, J = 8.0, 4.8 Hz, 1 H), 3.97
(s, 3 H).
Methyl 2-Bromobenzoate (3l)17
Colorless oil; yield: 4.87 g (91%).
1H NMR (400 MHz, CDCl3): δ = 7.80 (d, J = 6.8 Hz, 1 H), 7.67 (d,
J = 7.6 Hz, 1 H), 7.39 (m, 2 H), 3.94 (s, 3 H).
Methyl Thiophene-2-carboxylate (3y)4b
Colorless oil; yield: 2.95 g (83%).
1H NMR (400 MHz, CDCl3): δ = 7.81 (d, J = 3.2 Hz, 1 H), 7.56 (d,
J = 4.8 Hz, 1 H), 7.10 (t, J = 4.4 Hz, 1 H), 3.89 (s, 3 H).
Methyl 4-Formylbenzoate (3m)19
White solid; yield: 3.65 g (89%); mp 61–62 °C.
1H NMR (400 MHz, CDCl3): δ = 10.11 (s, 1 H), 8.22 (d, J = 8.4 Hz,
2 H), 7.97 (d, J = 8.4 Hz, 2 H), 3.97 (s, 3 H).
Allyl 2-Methoxybenzoate (3z)25
Colorless oil; yield: 4.42 g (92%).
1H NMR (400 MHz, CDCl3): δ = 7.84 (d, J = 7.6 Hz, 1 H), 7.47 (t,
J = 8.4 Hz, 1 H), 6.96–6.99 (m, 2 H), 5.99–6.08 (m, 1 H), 5.45 (d,
J = 17.2 Hz, 1 H), 5.29 (d, J = 10.4 Hz, 1 H), 4.81 (d, J = 5.6 Hz, 2
H), 3.91 (s, 3 H).
Ethyl Methyl Terephthalate (3n)20
White solid; yield: 4.58 g (88%); mp 34–35 °C.
1H NMR (400 MHz, CDCl3): δ = 8.10 (s, 4 H), 4.43 (q, J = 7.2 Hz,
2 H), 3.95 (s, 3 H), 1.43 (t, J = 7.2 Hz, 3 H).
Benzyl 2-Methoxybenzoate (3aa)26
Colorless oil; yield: 5.27 g (87%).
1H NMR (400 MHz, CDCl3): δ = 7.85 (d, J = 7.6 Hz, 1 H), 7.49–
7.45 (m, 3 H), 7.40–7.31 (m, 3 H), 6.99–6.90 (m, 2 H), 5.35 (s, 2 H),
3.91 (s, 3 H).
Methyl Trimethylacetate(3o)7i
Colorless oil; yield: 2.33 g (80%).
1H NMR (400 MHz, CDCl3): δ = 3.67 (s, 3 H), 1.20 (s, 9 H).
Methyl Cyclohexanecarboxylate (3p)21
Colorless oil; yield: 3.55 g (88%).
1H NMR (400 MHz, CDCl3): δ = 3.65 (s, 3 H), 2.34–2.26 (m, 1 H),
1.92–1.88 (m, 2 H), 1.77–1.72 (m, 2 H), 1.66–1.62 (m, 1 H), 1.48–
1.39 (m, 2 H), 1.30–1.22 (m, 3 H).
Methallyl 2-Methoxybenzoate (3ab)
Colorless oil; yield: 4.43 g (86%).
1H NMR (400 MHz, CDCl3): δ = 7.84 (d, J = 8.0 Hz, 1 H), 7.47 (t,
J = 7.6 Hz, 1 H), 6.97–7.00 (m, 2 H), 5.00 (d, J = 12 Hz, 2 H), 4.73
(s, 2 H), 3.91 (s, 3 H), 1.84 (s, 3 H).
13C NMR (100 MHz, CDCl3, TMS): δ = 163.4, 156.8, 137.6, 131.1,
129.2, 117.6, 117.5, 110.3, 109.5, 65.5, 53.4, 17.1.
HRMS (ESI): m/z [M + Na]+ calcd for C12H14O3Na: 229.0841,
found: 229.0835.
Methyl Tetradecanoate (3q)22
Colorless oil; yield: 5.75 g (95%).
1H NMR (400 MHz, CDCl3): δ = 3.67 (s, 3 H), 2.32 (t, J = 7.6 Hz,
2 H), 1.25–1.28 (m, 22 H), 0.90 (t, J = 6.0 Hz, 3 H).
Methyl 3-Phenylpropanoate (3r)7i
Colorless oil; yield: 3.53 g (86%).
Prop-2-ynyl 2-Methoxybenzoate (3ac)27
Colorless oil; yield: 3.8 g (80%).
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2014, 46, 263–268