The Journal of Organic Chemistry
Page 4 of 6
Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3): δ 200.6, 137.2,
133.0, 128.7, 128.2, 40.7, 17.9, 14.0.
2H), 3.16−3.11 (m, 2H), 2.43 (s, CH3); 13C{1H} NMR (75
MHz, CDCl3): δ 199.3, 139.4, 136.9, 136.0, 133.1, 130.4,
128.8, 128.6, 128.1, 126.4, 126.2, 39.1, 27.5, 19.4.
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1-Phenylnonan-3-one (4ab).5e 24 h of reaction; Colourless
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1-Phenyl-3-(p-tolyl)propan-1-one (4ca).19c16 h of reaction;
oil; Eluent: PE/EA = 24/1; 82% yield (89 mg); H NMR (400
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White solid; Eluent: PE/EA = 9/1; 81% yield (91 mg); H
MHz, CDCl3): δ 7.31−7.28 (m, 2H), 7.22−7.19 (m, 3H), 2.92
(t, J = 7.6 Hz, 2H), 2.74 (t, J = 7.6 Hz, 2H), 2.39 (t, J = 7.6 Hz,
2H), 1.54 (qu, J = 8.0 Hz, 2H), 1.28 (br, 6H), 0.90 (t, J = 6.9
Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3): δ 210.3, 141.3,
128.5, 128.4, 126.1, 44.3, 43.1, 31.7, 29.9, 29.0, 23.8, 22.6,
14.1.
NMR (300 MHz, CDCl3): δ 8.04 (d, J = 7.4 Hz, 2H), 7.62 (t, J
= 7.3 Hz, 1H), 7.52 (t, J = 7.5 Hz, 2H), 7.25−7.18 (m, 4H),
3.35 (t, J = 7.7 Hz, 2H), 3.12 (t, J = 7.6 Hz, 2H), 2.41 (s, 3H);
13C{1H} NMR (75 MHz, CDCl3): δ 199.3, 138.2, 136.9, 135.6,
133.0, 129.2, 128.6, 128.3, 128.1, 40.6, 29.7, 21.0.
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Hexadecan-7-one (4hb).6a 24 h of reaction; Colourless oil;
Eluent: PE/EA = 24/1; 65% yield (78 mg); H NMR (400
MHz, CDCl3): δ 2.36 (t, J = 7.4 Hz, 4H), 1.54 (qu, J = 7.2 Hz,
4H), 1.24 (br, 18H), 0.86 (t, J = 6.8 Hz, 6H); 13C{1H} NMR
(101 MHz, CDCl3): δ 211.7, 42.9, 32.0, 31.7, 29.6, 29.6, 29.4,
29.1, 24.0, 24.0, 22.8, 22.6, 14.2, 14.1.
3-(4-Fluorophenyl)-1-phenylpropan-1-one (4da).11a 18 h of
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reaction; White solid; Eluent: PE/EA = 9/1; 83% yield (95
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mg); H NMR (400 MHz, CDCl3): δ 7.96 (d, J = 7.3 Hz, 2H),
7.56 (t, J = 7.3 Hz, 1H), 7.45 (t, J = 7.6 Hz, 2H), 7.21 (dd, J1 =
8.3 Hz, J2 = 5.6 Hz, 2H), 6.98 (t, J = 8.7 Hz, 2H), 3.28 (t, J =
7.5 Hz, 2H), 3.05 (t, J = 7.5 Hz, 2H); 13C{1H} NMR (75 MHz,
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CDCl3): δ 199.0, 161.4 (d, JC-F = 243.7 Hz), 137.0 (d, JC-F
=
4-Phenylbutan-2-one (4ac).19g 24 h of reaction; Colourless
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3.2 Hz), 136.8, 133.1, 129.9 (d, JC-F = 7.8 Hz), 128.6, 128.0,
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115.2 (d, 2JC-F = 21.1 Hz), 40.4, 29.3.
oil; Eluent: PE/EA = 9/1; 78% yield (58 mg); H NMR (300
MHz, CDCl3): δ 7.31−7.26 (m, 2H), 7.21−7.17 (m, 3H),
2.93−2.86 (m, 2H), 2.80−2.73 (m, 2H), 2.14 (s, 3H); 13C{1H}
NMR (75 MHz, CDCl3): δ 208.0, 141.1, 128.6, 128.4, 126.2,
45.3, 30.2, 29.8.
3-(4-Methoxyphenyl)-1-phenylpropan-1-one (4ea).19c 16 h of
reaction; White solid; Eluent: PE/EA = 9/1; 88% yield (106
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mg); H NMR (400 MHz, CDCl3): δ 7.97 (d, J = 8.5 Hz, 2H),
7.56 (t, J = 8.0 Hz, 1H), 7.46 (t, J = 7.9 Hz, 2H), 7.18 (d, J =
8.7 Hz, 2H), 6.86 (d, J = 8.7 Hz, 2H), 3.8 (s, 3H), 3.28 (t, J =
7.7 Hz, 2H), 3.03 (t, J = 7.6 Hz, 2H); 13C{1H} NMR (101
MHz, CDCl3): δ 199.4, 158.1, 137.0, 133.4, 133.1, 129.4,
128.7, 128.1, 114.0, 55.4, 40.8, 29.4.
General Procedure for Cross Coupling of Alcohols
(Scheme 2,3).
1,5-Diphenylpentan-3-one (6a).19g 2-Propanol (1mL) and
benzyl alcohol (0.5 mmol) was reacted in presence of complex
Ru-1 (0.5 mol%) and NaOH (10 mol%) in toluene at 150 °C
for 24 h under argon atmosphere. Then the generated extra
acetone was removed from the reaction medium by applying
vacuum. Further the reaction mixture was reloaded with ben-
zyl alcohol (0.5 mmol), Ru-1 (0.5 mol%) and NaOH (10
mol%). Then the reaction mixture was heated at 150 °C for 24
h. After it was cooled to room temperature. Purification by
silica gel column chromatography (pet. ether : EtOAc = 9 : 1)
afforded the product as a colourless oil with 63% yield (75
mg). 1H NMR (400 MHz, CDCl3): δ 7.31−7.27 (m, 4H),
7.23−7.17 (m, 6H), 2.91 (t, J = 7.6 Hz, 4H), 2.73 (t, J = 7.6
Hz, 4H); 13C{1H} NMR (101 MHz, CDCl3): δ 209.2, 141.1,
128.6, 128.4, 126.2, 44.6, 29.8.
3-(Furan-2-yl)-1-phenylpropan-1-one (4fa).19c 20 h of reac-
tion; Pale yellow oil; Eluent: PE/EA = 9/1; 75% yield (75 mg);
1H NMR (400 MHz, CDCl3): δ 7.99−7.97 (m, 2H), 7.59−7.54
(m, 1H), 7.46 (t, J = 7.6 Hz, 1H), 7.31 (d, J = 1.7 Hz, 1H),
6.29 (dd, J1 = 3.1 Hz, J2 = 1.9 Hz, 2H), 6.06−6.05 (m, 2H),
3.34 (t, J = 7.4 Hz, 2H), 3.01 (t, J = 7.4 Hz, 2H); 13C{1H}
NMR (101 MHz, CDCl3): δ 198.8, 154.9, 141.2, 136.8, 133.3,
128.7, 128.1, 110.4, 105.4, 37.4, 22.6.
1,5-Diphenylpentan-1-one (4ga).19d 18 h of reaction; Colour-
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less oil; Eluent: PE/EA = 9/1; 83% yield (99 mg); H NMR
(400 MHz, CDCl3): δ 7.97−7.95 (m, 2H), 7.56 (t, J = 7.6 Hz,
1H), 7.47 (t, J = 7.6 Hz, 2H), 7.32−7.28 (m, 2H), 7.21 (d, J =
7.5 Hz, 3H), 3.00 (t, J = 7.1 Hz, 2H), 2.69 (t, J = 7.6 Hz, 2H),
1.86−1.69 (m, 4H); 13C{1H} NMR (101 MHz, CDCl3): δ
200.3, 142.3, 137.1, 133.0, 128.7, 128.5, 128.4, 128.1, 125.8,
38.5, 35.9, 31.2, 24.1.
1-Phenyl-5-(p-tolyl)pentan-3-one (6b).19h 2-Propanol (1mL)
and benzyl alcohol (0.5 mmol) was reacted in presence of
complex Ru-1 (0.5 mol%) and NaOH (10 mol%) in toluene at
150 °C for 24 h under argon atmosphere. Then the generated
extra acetone was removed from the reaction medium by
applying vacuum. Further to the reaction mixture 4-
methylbenzyl alcohol (0.5 mmol) was reloaded with, Ru-1
(0.5 mol%) and NaOH (10 mol%). Then the reaction mixture
was heated at 150 °C for 24 h. After it was cooled to room
temperature. Purification by silica gel column chromatography
(pet. ether : EtOAc = 9 : 1) afforded the product as a colour-
less oil with 60% yield (76 mg). 1H NMR (400 MHz, CDCl3):
δ 7.31 (t, J = 7.3 Hz, 2H), 7.25−7.19 (m, 3H), 7.11 (q, J = 8.1
Hz, 4H), 2.91 (dt, J1 = 14.4 Hz, J = 7.6 Hz, 4H), 2.76−2.70 (m,
4H), 2.35 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3): δ 209.2,
141.1, 138.0, 135.6, 129.2, 128.6, 128.4, 128.3, 126.2, 44.7,
44.6, 29.8, 29.4, 21.1.
1-Phenyldecan-1-one (4ha).19e 16 h of reaction; Colourless
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oil; Eluent: PE/EA = 9/1; 82% yield (95 mg); H NMR (300
MHz, CDCl3): δ 7.95 (dt, J1 = 7.1 Hz, J2 = 1.3 Hz, 2H),
7.55−7.50 (m, 1H), 7.46−7.40 (m, 2H), 2.94 (t, J = 7.4 Hz,
2H), 1.73 (qu, J = 7.4 Hz, 2H), 1.27 (br, 12H), 0.88 (t, J = 6.8
Hz, 3H); 13C{1H} NMR (75 MHz, CDCl3): δ 200.5, 137.2,
132.8, 128.6, 128.1, 38.6, 31.9, 29.6, 29.5, 29.4, 29.4, 24.4,
22.7, 14.2.
1-Phenylbutan-1-one (4ia).19f KOtBu was used instead of
NaOH; 24 h of reaction; Colourless oil; Eluent: PE/EA = 9/1;
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75% yield (56 mg); H NMR (400 MHz, CDCl3): δ 7.97−7.95
(m, 2H), 7.57−7.53 (m, 1H), 7.45 (t, J = 7.5 Hz, 2H), 2.95 (t, J
= 7.3 Hz, 2H), 1.77 (sextet, J = 7.4 Hz, 2H), 1.01 (t, J = 7.4
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