PAPER
Tin(II)-Catalyzed, Solvent-Free Kabachnik–Fields Reaction
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1H NMR (400 MHz, CDCl3): d = 1.02–1.10 (m, 3 H), 1.21–1.34 (m,
6 H), 2.01 (s, 1 H), 3.64–3.76 (m, 1 H), 3.82–3.97 (m, 1 H), 4.03–
4.24 (m, 4 H), 7.16–7.35 (m, 10 H).
13C NMR (100 MHz, CDCl3): d = 15.96, 16.02, 16.28, 16.29, 16.33,
22.15, 22.16, 24.64, 54.98, 55.10, 57.21, 58.71, 60.11, 62.47, 62.54,
62.68, 62.76, 62.80, 126.52, 126.81, 126.85, 126.95, 127.48,
127.51, 128.14, 128.16, 128.19, 128.22, 128.24, 128.36, 128.42,
136.35, 136.36, 143.90, 145.00.
HRMS: m/z [MH+] calcd for C19H26NO5P: 379.1621; found:
380.1619.
Diethyl (2-Furanyl)(N-phenylamino)methylphosphonate (3m)24
Obtained as a red-purple oil.
1H NMR (400 MHz, CDCl3): d = 1.17 (t, J = 7.01 Hz, 3 H), 1.25 (t,
J = 7.01 Hz, 3 H), 3.80–4.20 (m, 4 H), 4.91 (d, J = 23.88 Hz, 1 H),
6.28 (t, J = 3.12 Hz, 1 H), 6.38 (t, J = 3.2 Hz, 1 H), 6.65–6.73 (m,
4 H), 7.09–7.14 (m, 2 H), 7.34 (s, 1 H).
13C NMR (100 MHz, CDCl3): d = 15.89, 15.95, 16.03, 16.08, 49.04,
50.63, 62.95, 63.02, 63.17, 63.24, 108.44, 108.50, 110.45, 110.47,
113.61, 113.63, 118.53, 128.83, 128.85, 142.12, 142.50, 145.7,
146.88, 149.08, 149.10.
LRMS (EI): m/z = 346 [M+], 210 [M – P(O)(OEt)2].
Diethyl (4-Hydroxyphenyl)(N-phenylamino)methylphospho-
nate (3i)21
Obtained as an orange solid.
1H NMR (400 MHz, CDCl3): d = 1.10 (t, J = 7.09 Hz, 3 H), 1.24 (t,
J = 7.09 Hz, 3 H), 3.66–3.76 (m, 1 H), 3.88–3.98 (m, 1 H), 4.01–
4.16 (m, 2 H), 4.71 (d, J = 24.03 Hz, 1 H), 6.58–6.60 (m, 2 H), 6.67
(t, J = 7.4 Hz, 1 H), 6.73 (d, J = 8.24 Hz, 2 H), 7.08 (t, J = 8.46 Hz,
2 H), 7.21–7.23 (m, 2 H), 8.51 (s, 1 H).
LRMS (EI): m/z = 309 [M+], 172 [M – P(O)(OEt)2].
Diethyl (4-Chlorophenyl)(N-phenylamino)methylphosphonate
(3n)24
Obtained as a yellow-brown solid.
13C NMR (100 MHz, CDCl3): d = 16.04, 16.10, 16.21, 16.27, 54.26,
55.90, 63.43, 63.50, 63.57, 113.85, 115.81, 115.83, 118.34, 125.67,
125.7, 128.79, 128.84, 129.02, 146.02, 146.17, 156.64, 156.67.
1H NMR (400 MHz, CDCl3): d = 1.15 (t, J = 7.09 Hz, 3 H), 1.28 (t,
J = 7.09 Hz, 3 H), 3.72–4.18 (m, 4 H), 4.73 (d, J = 24.49 Hz, 1 H),
6.54–6.57 (m, 2 H), 6.68–6.72 (m, 1 H), 7.07–7.12 (m, 2 H), 7.29–
7.31 (m, 2 H), 7.39–7.42 (m, 2 H).
Diethyl (4-Methoxyphenyl)(N-phenylamino)methylphospho-
13C NMR (100 MHz, CDCl3): d = 16.16, 16.21, 16.33, 63.23, 53.43,
54.72, 56.22, 63.30, 63.33, 63.40, 113.78, 118.60, 118.74, 128.71,
128.74, 129.06, 129.11, 129.16, 129.36, 133.66, 134.53, 134.56,
145.89, 146.03, 152.64.
nate (3j)9
Obtained as a white solid.
1H NMR (400 MHz, CDCl3): d = 1.13 (t, J = 7.01 Hz, 3 H), 1.27 (t,
J = 7.09 Hz, 3 H), 3.64–4.17 (m, 4 H), 3.76 (s, 3 H), 4.71 (d,
J = 23.8 Hz, 1 H), 6.57–6.60 (m, 2 H), 6.66–6.70 (m, 1 H), 6.84–
6.87 (m, 2 H), 7.07–7.12 (m, 2 H), 7.36–7.40 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 16.16, 16.21, 16.32, 16.4, 54.54,
55.14, 56.05, 63.07, 63.11, 63.14, 63.18, 113.82, 113.96, 113.98,
118.27, 127.58, 127.63, 128.85, 128.91, 129.06, 146.20, 146.34,
159.20, 159.23.
LRMS (EI): m/z = 353 [M+], 216 [M – P(O)(OEt)2].
Diethyl (4-Bromophenyl)(N-phenylamino)methylphosphonate
(3o)32
Obtained as a grayish solid.
1H NMR (400 MHz, CDCl3): d = 1.16 (t, J = 7.0 Hz, 3 H), 1.28 (t,
J = 7.0 Hz, 3 H), 3.73–4.18 (m, 4 H), 4.71 (d, J = 24.8 Hz, 1 H),
6.53–6.56 (m, 2 H), 6.69–6.73 (m, 1 H), 7.08–7.13 (m, 2 H), 7.33–
7.36 (m, 2 H), 7.44–7.47 (m, 2 H).
LRMS (EI): m/z = 349 [M+], 212 [M – P(O)(OEt)2].
Diethyl (4-Methylphenyl)(N-phenylamino)methylphosphonate
13C NMR (100 MHz, CDCl3): d = 16.15, 16.21, 16.33, 16.39, 54.80,
56.29, 63.23, 63.30, 63.33, 63.39, 113.77, 118.59, 118.61, 121.75,
121.80, 129.16, 129.37, 129.39, 129.44, 131.62, 131.64, 131.67,
135.08, 135.11, 145.86, 146.01.
(3k)9
Obtained as a white-yellow solid.
1H NMR (400 MHz, CDCl3): d = 1.12 (t, J = 7.09 Hz, 3 H), 1.27 (t,
J = 7.09 Hz, 3 H), 2.29 (s, 3 H), 3.63–4.16 (m, 4 H), 4.73 (d,
J = 24.1 Hz, 1 H), 6.59 (d, J = 7.7 Hz, 2 H), 6.67 (t, J = 7.4 Hz,
1 H), 7.06–7.13 (m, 3 H), 7.33–7.35 (m, 3 H).
13C NMR (100 MHz, CDCl3): d = 16.08, 16.14, 16.29, 16.35, 21.07,
21.02, 22.71, 22.73, 54.86, 56.36, 63.05, 63.07, 63.09, 63.14, 63.17,
113.74, 118.19, 127.59, 127.62, 127.64, 129.02, 129.16, 129.18,
129.20, 132.59, 132.62, 137.44, 137.47, 146.20, 146.36.
LRMS (EI): m/z = 397 [M+], 260 [M – P(O)(OEt)2].
Diethyl (4-Nitrophenyl)(N-phenylamino)methylphosphonate
(3p)21
Obtained as an orange solid.
1H NMR (400 MHz, CDCl3): d = 1.18 (t, J = 7.09 Hz, 3 H), 1.29 (t,
J = 7.0 Hz, 3 H), 3.83–4.21 (m, 4 H), 4.86 (d, J = 25.48 Hz, 1 H),
6.52–6.55 (m, 2 H), 6.71–6.75 (m, 1 H), 7.08–7.13 (m, 2 H), 7.64–
7.68 (m, 2 H), 8.17–8.21 (m, 2 H).
LRMS (EI): m/z = 333 [M+], 196 [M – P(O)(OEt)2].
Diethyl (2,4-Dimethoxyphenyl)(N-phenylamino)methylphos-
phonate (3l)
Obtained as a white-pink solid; mp 100–103 °C.
13C NMR (100 MHz, CDCl3): d = 16.16, 16.34, 16.38, 16.4, 54.84,
55.23, 56.73, 63.16, 63.41, 63.48, 63.69, 63.75, 113.77, 119.05,
123.69, 128.58, 128.61, 128.63, 129.30, 129.32, 129.39, 141.29,
144, 144.04, 145.52, 145.66, 147.58.
1H NMR (400 MHz, CDCl3): d = 1.06 (t, J = 7.09 Hz, 3 H), 1.30 (t,
J = 7.09 Hz, 3 H), 3.59–3.68 (m, 1 H), 3.75 (s, 3 H), 3.85–3.95 (m,
1 H), 3.89 (s, 3 H), 4.12–4.21 (m, 2 H), 4.78 (br s, 1 H), 5.28 (d,
J = 24.26 Hz, 1 H), 6.42–6.45 (m, 2 H), 6.57–6.67 (m, 3 H), 7.05–
7.11 (m, 2 H), 7.35–7.38 (m, 1 H).
13C NMR (100 MHz, CDCl3): d = 16.08, 16.10, 16.33, 55.19, 55.62,
62.84, 62.91, 62.96, 63.04, 96.4, 98.31, 98.33, 104.7, 104.73,
113.51, 116.67, 117.97, 128.81, 129, 129.02, 146.17, 146.32,
158.12, 160.37, 160.40.
LRMS (EI): m/z = 364 [M+], 227 [M – P(O)(OEt)2].
Diethyl (2-Naphthyl)(N-phenylamino)methylphosphonate (3q)9
Obtained as a yellowish solid.
1H NMR (400 MHz, CDCl3): d = 1.07 (t, J = 7.09 Hz, 3 H), 1.27 (t,
J = 7.0 Hz, 3 H), 3.61–4.18 (m, 4 H), 4.92 (d, J = 24.18 Hz, 1 H),
6.61–6.68 (m, 3 H), 7.04–7.09 (m, 2 H), 7.40–7.46 (m, 2 H), 7.58–
7.61 (m, 1 H), 7.77–7.82 (m, 3 H), 7.93 (s, 1 H).
LRMS (EI): m/z = 379 [M+], 241 [M – P(O)(OEt)2].
13C NMR (100 MHz, CDCl3): d = 16.06, 16.12, 16.30, 16.36, 55.48,
56.96, 63.16, 63.23, 65.72, 113.79, 118.34, 125.50, 125.54, 125.93,
Synthesis 2010, No. 1, 57–62 © Thieme Stuttgart · New York