mmol) of recovered 1 (Ph). The fifth eluate (toluene-ethyl ace-
tate 2:1) gave 0.23 g (0.55 mmol) of 4 (Ph3). The sixth eluate
(toluene-ethyl acetate 1:2) gave 0.34 g (0.98 mmol) of 8 (Ph3).
11 (Ph3): Colorless oil. 1H NMR: ¤ 1.72 (3H, s), 1.83 (3H, s),
3.86 (1H, d, J = 8.2 Hz), 4.36 (1H, d, J = 8.2 Hz), 5.05 (1H, d,
J = 1.0 Hz), 5.99 (1H, d, J = 1.0 Hz), 7.0-7.6 (13H, m), 7.7
(2H, m). 13C NMR: ¤ 23.8 (q), 23.9 (q), 62.4 (s), 75.8 (t), 96.8
(d), 111.6 (d), 111.9 (d), 124.9 (d), 125.9 (d), 127.3 (d), 127.6
(d), 128.2 (d), 128.3 (d), 128.6 (d), 129.1 (d), 129.3 (d), 133.7
(s), 137.8 (s), 138.0 (s), 138.9 (s), 150.9 (s), 170.4 (s). HRMS
(FAB) found: m/z 423.1857 [M]+; calcd for C28H25NO3: m/z
423.1834.
Found: C, 77.38; H, 7.25; N, 3.42%. Calcd for C26H29NO3: C,
77.39; H, 7.24; N, 3.47%.
8 (Ph, t-Bu, Ph): Mp 159-161 °C (colorless needles from
chloroform-hexane). IR: 3346 (br), 2972, 2868, 1693, 1637,
1485, 1444, 1392, 1365, 1265, 1078, 1055, 978, 870, 770, 716,
1
706 cm¹1. H NMR: ¤ 0.17 (9H, s), 1.07 (3H, s), 1.52 (3H, s),
3.48 (1H, dd, J = 6.5 and 11.9 Hz), 4.02 (1H, dd, J = 4.1 and
11.9 Hz), 5.70 (1H, dd, J = 4.1 and 6.5 Hz), 6.60 (1H, s), 7.31-
7.43 (8H, m), 7.47-7.51 (2H, m). 13C NMR: ¤ 26.9 (q), 27.3
(q), 28.7 (q), 44.6 (s), 70.6 (s), 72.0 (t), 120.4 (d), 127.5 (d),
127.8 (s), 128.5 (d), 128.6 (d), 129.4 (d), 129.6 (d), 129.7 (d),
130.7 (d), 132.7 (d), 136.0 (s), 136.8 (s), 144.5 (s), 149.0 (s),
168.1 (s), 213.8 (s). Found: C, 77.35; H, 7.32; N, 3.49%. Calcd
for C26H29NO3: C, 77.39; H, 7.24; N, 3.47%.
9 (Ph3): Mp 190-193 °C (Colorless needles from chloro-
form-hexane). IR: 3057, 2983, 2968, 2885, 1653, 1595, 1446,
1
1398, 1277, 1024, 922, 775, 710, 698, 687 cm¹1. H NMR: ¤
1-(1-Methyl-2-hydroxyethyl)-4,6-diphenyl-2-pyridone (12):
Mp 139.5-140 °C (Colorless needles from chloroform-hexane).
IR: 3294, 3056, 3010, 1639, 1583, 1560, 1537, 1491, 1479,
1448, 1390, 1360, 1263, 1153, 1080, 1065, 1036, 1026, 984,
1.55 (3H, s), 1.68 (3H, s), 3.48 (1H, d, J = 20.1 Hz), 3.52 (2H,
d, J = 8.9 Hz), 3.57 (1H, d, J = 20.1 Hz), 3.79 (2H, d, J =
8.9 Hz), 7.04-7.11 (5H, m), 7.18 (2H, t, J = 7.7 Hz), 7.32 (1H,
t, J = 7.4 Hz), 7.35-7.44 (3H, m), 7.62 (2H, d, J = 7.4 Hz),
7.70 (2H, d, J = 7.2 Hz). 13C NMR: ¤ 23.0 (q), 24.8 (q), 41.0
(t), 60.9 (s), 77.3 (t), 97.1 (s), 126.6 (d), 128.0 (d), 128.1 (d),
128.3 (d), 128.5 (d), 128.7 (d), 128.8 (d), 129.4 (d), 132.9 (d),
135.8 (s), 136.9 (s), 137.1 (s), 137.4 (s), 140.1 (s), 166.0 (s),
195.3 (s). Found: C, 79.55; H, 6.00; N, 3.22%. Calcd for
C28H25NO3: C, 79.41; H, 5.95; N, 3.31%.
1
874, 858, 775, 762, 748, 698, 669, 635 cm¹1. H NMR: ¤ 1.35
(6H, s), 3.85 (2H, d, J = 5.5 Hz), 5.94 (1H, t, J = 5.5 Hz), 6.38
(1H, d, J = 2.2 Hz), 6.78 (1H, d, J = 2.2 Hz), 7.41-7.47 (3H,
m), 7.43 (5H, s), 7.60-7.62 (2H, m). 13C NMR: ¤ 28.1 (q), 69.8
(s), 72.3 (t), 113.1 (d), 116.7 (d), 126.7 (d), 128.0 (d), 128.5 (d),
128.8 (d), 128.9 (d), 129.7 (d), 136.4 (s), 140.2 (s), 149.7 (s),
150.8 (s), 169.3 (s). Found: C, 78.80; H, 6.61; N, 4.23%. Calcd
for C21H21NO2: C, 78.97; H, 6.63; N, 4.39%.
8 (Ph3): Mp 157-159 °C (Colorless needles from chloro-
form-hexane). IR: 3321 (br), 1672, 1641, 1602, 1587, 1516,
1485s, 1392, 1273s, 1153, 1076, 1057, 955, 870, 775, 704
Similarly the following products were isolated from reaction
of 1 with 2 in acetonitrile.
1
cm¹1. H NMR: ¤ 1.36 (6H, s), 3.81 (2H, d, J = 5.5 Hz), 5.36
7 (i-Pr, i-Pr, Ph): An enol tautomer. Mp 137.5-138.5 °C
(Colorless needles from hexane). IR: 2970, 2931, 2872, 1643,
1587, 1470, 1363, 1354, 1302, 1205, 1101, 991, 970, 926, 771
(1H, t, J = 5.5 Hz), 6.63 (1H, s), 7.0-7.5 (15H, m). 13C NMR: ¤
28.1 (broad q), 70.8 (s), 72.2 (t), 120.4 (d), 124.6 (s), 127.6 (d),
128.0 (d), 128.3 (d), 128.5 (d), 128.7 (d), 128.8 (d), 129.3 (d),
132.8 (d), 135.6 (s), 136.4 (s), 147.5 (s), 150.8 (s), 168.1 (s),
195.5 (s). Found: C, 79.25; H, 6.08; N, 3.21%. Calcd for
C28H25NO3: C, 79.41; H, 5.95; N, 3.31%.
1
cm¹1. H NMR: ¤ 0.90 (6H, d, J = 6.9 Hz), 1.03 (6H, d, J =
6.9 Hz), 1.20 (6H, s), 2.54 (2H, septet, J = 6.9 Hz), 3.92 (2H,
s), 6.82 (1H, s), 7.36-7.42 (3H, m), 7.53-7.57 (2H, m), 17.36
(1H, s). 13C NMR: ¤ 19.34 (q), 28.3 (q), 33.7 (d), 66.3 (s), 79.1
(t), 108.1 (d), 117.6 (d), 126.8 (d), 128.8 (s), 129.3 (s), 139.5
(s), 144.8 (s), 161.2 (s), 197.3 (s). Found: C, 74.11; H, 8.47; N,
3.75%. Calcd for C22H29NO3: C, 74.33; H, 8.22; N, 3.94%.
7 (t-Bu, t-Bu, Ph): A keto tautomer. Mp 131-131.5 °C
(colorless needles from hexane). IR: 3055, 2964, 1705, 1684,
1614, 1481, 1360, 1267, 1192, 1153, 1074, 897, 762, 690
cm¹1. 1H NMR: ¤ 1.08 (18H, s), 1.34 (6H, s), 3.93 (2H, s), 6.24
(1H, s), 7.27-7.30 (3H, m), 7.33 (1H, s), 7.43-7.45 (2H, m).
13C NMR: ¤ 27.4 (q), 28.6 (q), 45.1 (s), 63.6 (d), 68.0 (s), 77.6
(t), 117.0 (d), 128.0 (d), 128.6 (d), 129.5 (d), 139.6 (s), 149.0
(s), 160.2 (s), 213.8 (s). Found: C, 75.44; H, 8.81; N, 3.64%.
Calcd for C24H33NO3: C, 75.16; H, 8.67; N, 3.65%.
Reaction of 1 (Ph) with 2 (t-Bu, Ph) in Acetonitrile
(Table 1, Run 4). Similar treatment of 3 mmol of 1 (Ph) with
3.3 mmol of 2 (t-Bu, Ph) gave the following products. The first
toluene eluate was the recovered acetylene and other unidenti-
fied materials. The second toluene eluate was 40 mg (0.10
mmol) of 11 (Ph, t-Bu, Ph). The second toluene eluate was 10
mg (0.03 mmol) of 9 (Ph, t-Bu, Ph). The third toluene eluate
was 0.19 g of a mixture of 1 (Ph) (0.49 mmol) and 8 (Ph, t-Bu,
Ph) (0.21 mmol). The ratio of the products was determined by
the 1H NMR spectrum of the mixture. The fourth toluene-ethyl
acetate (2:1) eluate gave 0.53 g of a mixture of 8 (Ph, t-Bu,
Ph) (1.14 mmol) and 3 (Ph, t-Bu, Ph) (0.17 mmol). The fifth
toluene-ethyl acetate (1:2) eluate gave 0.16 g of a mixture of 8
(Ph, t-Bu, Ph) (0.33 mmol) and 12 (Ph2) (0.08 mmol).
11 (Ph, t-Bu, Ph): Mp 107-109 °C (colorless needles from
chloroform-hexane). IR: 3062, 2972, 2881, 1660, 1643, 1589,
1446, 1383, 1362, 1311, 1093, 1028, 1001, 985, 972, 870, 756,
731, 698 cm¹1. 1H NMR: ¤ 1.27 (9H, s), 1.69 (3H, s), 1.77 (3H,
s), 3.78 (1H, d, J = 8.1 Hz), 4.20 (1H, d, J = 8.1 Hz), 4.84 (1H,
d, J = 1.0 Hz), 5.36 (1H, d, J = 1.0 Hz), 6.59-6.92 (2H, m),
7.14-7.25 (6H, m), 7.32-7.35 (2H, m). 13C NMR: ¤ 23.8 (q),
24.0 (q), 28.0 (q), 35.3 (s), 62.3 (s), 75.7 (t), 94.3 (d), 110.9 (d),
111.4 (s), 125.9 (d), 127.2 (d), 127.5 (d), 127.9 (d), 128.1 (d),
129.1 (d), 138.2 (s), 138.3 (s), 138.6 (s), 162.0 (s), 170.0 (s).
8 (Ph, i-Pr, Ph): Mp 137.5-138 °C (colorless needles from
hexane). IR: 3348 (br), 2970, 1699, 1645, 1485, 1446, 1385,
1
1057, 993, 868, 771, 706 cm¹1. H NMR: ¤ 0.25 (6H, d, J =
6.9 Hz), 1.31 (6H, s), 1.65 (1H, septet, J = 6.9 Hz), 3.76 (2H,
broad d, J = 5.2 Hz), 5.65 (1H, broad t, J = 5.2 Hz), 6.01 (1H,
s), 7.34-7.43 (10H, m). 13C NMR: ¤ 17.4 (q), 28.1 (q), 42.3 (d),
70.7 (s), 72.0 (t), 120.6 (d), 127.1 (s), 127.8 (d), 128.5 (d), 129.0
(d), 129.2 (d), 129.6 (d), 131.2 (d), 135.8 (s), 136.7 (s), 146.2
(s), 149.5 (s), 168.1 (s), 208.8 (s). Found: C, 77.09; H, 7.05; N,
3.47%. Calcd for C25H27NO3: C, 77.09; H, 6.99; N, 3.60%.
9 (Ph, i-Pr, Ph): Mp 150-151 °C (colorless needles from
hexane). IR: 3058, 2976, 1693, 1666, 1446, 1398, 1200, 1034,
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