Job/Unit: O21673
/KAP1
Date: 19-03-13 16:49:22
Pages: 9
Y. Masuyama, M. Hayashi, N. Suzuki
FULL PAPER
NMR (75 MHz, CDCl3): δ = 42.3, 55.2, 85.0, 89.9, 114.0, 123.2,
128.1, 128.2, 128.6, 128.8, 129.1, 131.6, 132.6, 133.4, 140.6, (3ec): Rf = 0.77 (hexane/ethyl acetate = 3:1). H NMR (300 MHz,
2,6-Di-tert-butyl-4-[1-(2-phenylethyl)-3-phenyl-2-propynyl]phenol
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158.6 ppm.
CDCl3): δ = 1.45 (s, 18 H), 2.07–2.17 (m, 2 H), 2.76–2.97 (m, 2 H),
3.77 (t, J = 7.3 Hz, 1 H), 5.10 (s, 1 H), 7.16–7.32 (m, 8 H), 7.18 (s,
2 H), 7.44–7.48 (m, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
30.3, 33.9, 34.4, 37.8, 40.3, 83.7, 92.0, 124.0, 125.8, 127.6, 128.2,
128.3, 128.5, 131.6, 132.4, 135.8, 141.9, 152.5 ppm. HRMS (EI):
calcd. for C31H36O 424.2766; found 424.2785.
2,6-Di-tert-butyl-4-[1-(4-chlorophenyl)-3-phenyl-2-propynyl]phenol
(3cc): Rf = 0.73 (hexane/ethyl acetate = 3:1). H NMR (300 MHz,
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CDCl3): δ = 1.42 (s, 18 H), 5.09 (s, 1 H), 5.14 (s, 1 H), 7.23 (s, 2
H), 7.25–7.32 (m, 5 H), 7.37 (d, J = 8.1 Hz, 2 H), 7.42–7.47 (m, 2
H) ppm. 13C NMR (75 MHz, CDCl3): δ = 30.2, 34.4, 43.0, 84.8,
90.5, 123.5, 124.4, 127.9, 128.2, 128.6, 129.2, 131.5, 131.6, 132.4,
136.0, 140.9, 152.8 ppm. HRMS (EI): calcd. for C29H3135ClO
430.2063; found 430.2058.
2-(1-Phenyl-2-propynyl)-1,3-diphenyl-1,3-propanedione (5ab):[25b] Rf
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= 0.35 (hexane/ethyl acetate = 3:1). H NMR (300 MHz, CDCl3):
δ = 2.18 (d, J = 2.7 Hz, 1 H), 4.96 (dd, J = 9.9, 2.7 Hz, 1 H), 5.83
(d, J = 9.9 Hz, 1 H), 7.10–7.31 (m, 5 H), 7.40–7.47 (m, 5 H), 7.53–
7.58 (m, 1 H), 7.69 (d, J = 7.2 Hz, 2 H), 8.01 (d, J = 7.2 Hz, 2
H) ppm.
3-(1,3-Diphenyl-2-propynyl)-2,4-pentanedione (5ba):[25b] Rf = 0.33
(hexane/ethyl acetate = 3:1). 1H NMR (300 MHz, CDCl3): δ = 1.91
(s, 3 H), 2.37 (s, 3 H), 4.22 (d, J = 10.8 Hz, 1 H), 4.67 (d, J =
10.8 Hz, 1 H), 7.24–7.42 (m, 10 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 28.7, 31.0, 38.0, 75.5, 84.8, 88.0, 122.6, 127.7, 128.1,
128.2, 128.3, 128.8, 131.6, 138.1, 201.4, 201.5 ppm.
2-[1-(4-Chlorophenyl)-3-phenyl-2-propynyl]-5-methylthiophene (3cg):
Rf = 0.73 (hexane/ethyl acetate = 3:1). 1H NMR (300 MHz,
CDCl3): δ = 2.39 (s, 3 H), 5.29 (s, 1 H), 6.55 (d, J = 3.6 Hz, 1 H),
6.75 (d, J = 3.6 Hz, 1 H), 7.27–7.31 (m, 3 H), 7.30 (d, J = 8.7 Hz,
2 H), 7.39 (d, J = 8.7 Hz, 2 H), 7.42–7.49 (m, 2 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 15.3, 38.6, 84.6, 88.9, 123.0, 124.6, 124.9,
128.2, 128.6, 128.8, 129.0, 131.7, 133.1, 139.6, 139.8, 142.5 ppm.
HRMS (EI): calcd. for C20H1535ClS 322.0583; found 322.0588.
1-Methoxy-4-(1-phenyl-2-nonynyl)benzene (3da): Rf = 0.70 (hexane/
ethyl acetate = 3:1). H NMR (300 MHz, CDCl3): δ = 0.88 (t, J =
6.9 Hz, 3 H), 1.24–1.60 (m, 8 H), 2.26 (td, J = 6.9, 2.4 Hz, 2 H),
3.74 (s, 3 H), 4.91 (t, J = 2.4 Hz, 1 H), 6.81 (d, J = 9.0 Hz, 2 H),
7.15–7.37 (m, 7 H) ppm. HRMS (EI): calcd. for C22H26O 306.1984;
found 306.1987.
2-(1,3-Diphenyl-2-propynyl)-1,3-diphenyl-1,3-propanedione
(5bb):[25b] Rf = 0.40 (hexane/ethyl acetate = 3:1). 1H NMR
(300 MHz, CDCl3): δ = 5.19 (d, J = 9.9 Hz, 1 H), 5.93 (d, J =
9.9 Hz, 1 H), 6.98–7.03 (m, 2 H), 7.09–7.18 (m, 4 H), 7.21–7.30 (m,
4 H), 7.37–7.49 (m, 3 H), 7.52–7.59 (m, 3 H), 7.75 (d, J = 7.5 Hz,
2 H), 8.12 (d, J = 7.5 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 38.7, 63.0, 85.0, 89.3, 122.8, 127.4, 127.9, 128.4, 128.5, 128.6,
128.8, 129.0, 131.3, 133.4, 133.5, 136.4, 136.9, 139.2, 192.5,
193.3 ppm. HRMS (EI): calcd. for C30H22O2 414.1620; found
414.1626.
Ethyl 2-(1,3-Diphenyl-2-propynyl)-3-oxobutanoate (5bc):[25b] A mix-
ture of two diastereomers in a diastereomeric ratio of 55:45. Rf =
0.40 (hexane/ethyl acetate = 3:1). 1H NMR (300 MHz, CDCl3):
isomer 1: δ = 1.03 (t, J = 7.2 Hz, 3 H), 2.41 (s, 3 H), 3.98 (q, J =
7.2 Hz, 2 H), 4.00 (d, J = 10.2 Hz, 1 H), 4.62 (d, J = 10.2 Hz, 1
H), 7.20–7.50 (m, 10 H); isomer 2: δ = 1.27 (t, J = 7.2 Hz, 3 H),
2.00 (s, 3 H), 4.06 (d, J = 10.2 Hz, 1 H), 4.25 (q, J = 7.2 Hz, 2 H),
4.65 (d, J = 10.2 Hz, 1 H), 7.20–7.50 (m, 10 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 13.7, 14.1, 29.7, 30.5, 37.7, 37.8, 61.5, 61.7,
66.5, 66.7, 84.0, 84.6, 88.1, 88.4, 122.7, 123.0, 127.55, 127.59, 128.0,
128.11, 128.14, 128.16, 128.24, 128.55, 128.65, 131.5, 138.1, 138.2,
166.7, 167.0, 200.2, 200.7 ppm.
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1,2,3-Trimethoxy-4-(1-phenyl-2-nonynyl)benzene (3db): Rf = 0.60
(hexane/ethyl acetate = 3:1). 1H NMR (300 MHz, CDCl3): δ = 0.88
(t, J = 6.9 Hz, 3 H), 1.24–1.59 (m, 8 H), 2.24 (td, J = 7.2, 2.4 Hz,
2 H), 3.73 (s, 3 H), 3.80 (s, 3 H), 3.83 (s, 3 H), 5.31 (t, J = 2.4 Hz,
1 H), 6.63 (d, J = 8.7 Hz, 1 H), 7.12–7.28 (m, 4 H), 7.37 (d, J =
7.5 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 13.9, 18.8,
22.5, 28.5, 28.9, 31.2, 36.3, 55.8, 60.5, 60.6, 81.0, 84.0, 107.1, 123.0,
126.2, 127.6, 128.1, 128.6, 141.9, 142.7, 150.8, 152.5 ppm. HRMS
(EI): calcd. for C24H30O3 366.2195; found 366.2190.
2,6-Di-tert-butyl-4-(1-phenyl-2-nonynyl)phenol (3dc): Rf = 0.70 (hex-
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ane/ethyl acetate = 3:1). H NMR (300 MHz, CDCl3): δ = 0.88 (t,
J = 6.9 Hz, 3 H), 1.25–1.60 (m, 8 H), 1.40 (s, 18 H), 2.27 (td, J =
6.9, 2.1 Hz, 2 H), 4.89 (br., 1 H), 5.06 (s, 1 H), 7.14–7.19 (m, 1 H),
7.19 (s, 2 H), 7.27 (t, J = 7.5 Hz, 2 H), 7.38 (d, J = 7.5 Hz, 2
H) ppm. 13C NMR (75 MHz, CDCl3): δ = 14.1, 19.0, 22.6, 28.6,
29.0, 30.3, 31.4, 34.4, 43.2, 81.4, 84.6, 124.4, 126.4, 127.7, 128.3,
132.8, 135.6, 143.1, 152.4 ppm. HRMS (EI): calcd. for C29H40O
404.3079; found 404.3092.
3-(1-Phenyl-2-nonynyl)-2,4-pentanedione (5da): Rf = 0.53 (hexane/
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ethyl acetate = 3:1). H NMR (300 MHz, CDCl3): δ = 0.88 (t, J =
6.6 Hz, 3 H), 1.17–1.50 (m, 8 H), 1.87 (s, 3 H), 2.15 (td, J = 6.9,
2.4 Hz, 2 H), 2.33 (s, 3 H), 4.08 (d, J = 11.1 Hz, 1 H), 4.41 (dt, J
= 11.1, 2.4 Hz, 1 H), 7.18–7.35 (m, 5 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 14.0, 18.6, 22.5, 28.4, 28.6, 31.1, 31.2, 37.7, 76.0, 78.6,
85.4, 127.4, 127.9, 128.7, 138.8, 201.89, 201.92 ppm. HRMS (EI):
calcd. for C20H26O2 298.1933; found 298.1930.
2-(1-Phenyl-2-nonynyl)pyrrole (3dd): Rf = 0.73 (hexane/ethyl acetate
= 3:1). 1H NMR (300 MHz, CDCl3): δ = 0.89 (t, J = 6.9 Hz, 3 H),
1.26–1.60 (m, 8 H), 2.26 (dt, J = 7.5, 2.4 Hz, 2 H), 5.02 (br., 1 H),
5.94 (br., 1 H), 6.11 (dd, J = 6.0, 3.0 Hz, 1 H), 6.66 (m, 1 H), 7.20–
7.40 (m, 5 H), 8.15 (br., 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ
= 14.0, 18.9, 22.5, 28.6, 28.8, 31.3, 36.7, 79.0, 84.5, 106.0, 108.6,
116.9, 127.0, 127.6, 128.5, 131.4, 140.9 ppm. HRMS (EI): calcd.
for C19H23N 265.1830; found 265.1831.
3-(1-Phenyl-2-nonynyl)-1,3-diphenyl-1,3-propanedione (5db): Rf =
1
0.42 (hexane/ethyl acetate = 3:1). H NMR (300 MHz, CDCl3): δ
= 0.83 (t, J = 6.9 Hz, 3 H), 1.05–1.24 (m, 8 H), 1.88–1.96 (m, 2
H), 4.96 (br. d, J = 10.2 Hz, 1 H), 5.84 (dd, J = 10.2, 1.5 Hz, 1 H),
7.06–7.13 (m, 1 H), 7.16–7.26 (m, 4 H), 7.33–7.40 (m, 1 H), 7.41–
7.58 (m, 5 H), 7.71 (d, J = 7.8 Hz, 2 H), 8.09 (d, J = 7.8 Hz, 2
H) ppm. 13C NMR (75 MHz, CDCl3): δ = 14.0, 18.6, 22.4, 28.3,
31.2, 38.3, 63.4, 79.7, 85.5, 127.1, 128.3, 128.4, 128.5, 128.6, 129.0,
133.2, 133.3, 136.5, 137.0, 139.8, 192.7, 193.4 ppm. C30H30O2
(422.57): calcd. C 85.27, H 7.16; found C 84.97, H 6.95.
1,2,3-Trimethoxy-4-[1-(2-phenylethyl)-3-phenyl-2-propynyl]benzene
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(3eb): Rf = 0.55 (hexane/ethyl acetate = 3:1). H NMR (300 MHz,
CDCl3): δ = 2.04–2.15 (m, 2 H), 2.76–2.97 (m, 2 H), 3.83 (s, 3 H),
3.85 (s, 3 H), 3.86 (s, 3 H), 4.15 (t, J = 7.2 Hz, 1 H), 6.67 (d, J =
8.7 Hz, 1 H), 7.14–7.34 (m, 9 H), 7.44–7.50 (m, 2 H) ppm. 13C
NMR (125 MHz, CDCl3): δ = 31.4, 33.9, 39.0, 56.0, 60.7, 61.0,
82.8, 91.9, 107.3, 122.6, 123.9, 125.8, 127.7, 127.9, 128.2, 128.3,
128.5, 131.6, 141.8, 142.1, 150.9, 152.6 ppm. HRMS (EI): calcd.
for C26H26O3 386.1882; found 386.1894.
N-(1-Phenyl-2-propynyl)benzenesulfonamide (7aa): Rf = 0.23 (hex-
ane/ethyl acetate = 3:1). 1H NMR (500 MHz, CDCl3): δ = 2.29 (d,
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