The Journal of Organic Chemistry
Article
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58.5 °C. H NMR (400 MHz, CDCl3, ppm): δ 7.57 (d, J = 8.0, 2H),
[M]+. Anal. Calcd for C15H14O2: C, 79.62; H, 6.24. Found: C, 79.36;
H, 6.16.
7.54−7.44 (m, 4H), 7.36−7.27 (m, 2H). 13C{1H} NMR (100 MHz,
CDCl3, ppm): δ 193.8, 163.7, 161.2, 139.0, 138.9, 132.7, 130.1, 128.4,
125.8, 125.7, 119.9, 119.7, 116.8, 116.5. MS: m/z 218 [M]+. Anal.
Calcd for C13H8F2O: C, 71.56; H, 3.70. Found: C, 71.86; H, 3.94.
Bis(4-chlorophenyl)methanone (3p).14a Acetophenone (0.18 g,
1.5 mmol) and 4-chlorobromobenzene (0.58 g, 3.0 mmol) were used.
The product was obtained as a white solid (0.17 g, 45%). Mp: 148.1−
(4-Methoxyphenyl)-m-tolylmethanone (4c). Acetophenone (0.18
g, 1.5 mmol) and 3-bromotoluene (0.26 g, 1.5 mmol) and 4-
bromoanisole (0.28 g, 1.5 mmol) were used. The product was
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obtained as a pale yellow oil (0.17 g, 50%). H NMR (400 MHz,
CDCl3, ppm): δ 7.82 (d, J = 8.8 Hz, 2H), 7.57 (s, 1H), 7.53 (d, J = 6.8
Hz, 2H), 7.35 (d, J = 7.0 Hz, 2H), 6.96 (d, J = 8.8 Hz, 2H), 3.88 (s,
3H), 2.41 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, ppm): δ 195.7,
163.1, 138.2, 138.0, 132.6, 132.5, 130.2, 130.1, 127.9, 126.9, 113.4,
55.4, 21.3. MS: m/z 226 [M]+. Anal. Calcd for C15H14O2: C, 79.62; H,
6.24. Found: C, 79.38; H, 6.02.
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149.0 °C. H NMR (400 MHz, CDCl3, ppm): δ 7.73 (d, J = 8.0 Hz,
4H), 7.47 (d, J = 8.0 Hz, 4H). 13C{1H} NMR (100 MHz, CDCl3,
ppm): δ 194.2, 139.1, 135.4, 131.3, 128.7. MS: m/z 250 [M]+. Anal.
Calcd for C13H8Cl2O: C, 62.18; H, 3.21. Found: C, 62.03; H, 3.44.
Bis(4-(trifluoromethyl)phenyl)methanone (3q).15 Acetophenone
(0.18 g, 1.5 mmol) and 4-(trifluoromethyl)bromobenzene (1.15 g,
5.09 mmol) were used. The product was obtained as a white solid
(4-Methoxyphenyl)-o-tolylmethanone (4d).12a Acetophenone
(0.18 g, 1.5 mmol) and 2-bromotoluene (0.26 g, 1.5 mmol) and 4-
bromoanisole (0.28 g, 1.5 mmol) were used. The product was
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obtained as a pale yellow oil (0.11 g, 32%). H NMR (400 MHz,
(0.15 g, 32%). Mp: 103.9−104.8 °C. H NMR (400 MHz, CDCl3,
ppm): δ 7.91 (d, J = 8.0 Hz, 4H), 7.86−7.73 (m, 4H). 13C{1H} NMR
(100 MHz, CDCl3, ppm): δ 194.4, 139.7, 134.5, 133.1, 130.2, 130.1,
128.5, 125.6, 125.6, 122.1. MS: m/z 318 [M]+.
CDCl3, ppm): δ 7.79 (d, J = 8.9 Hz, 2H), 7.40−7.33 (m, 1H), 7.31−
7.20 (m, 3H), 6.93 (d, J = 8.9 Hz, 2H), 3.87 (s, 3H), 2.30 (s, 3H).
13C{1H} NMR (101 MHz, CDCl3, ppm): δ 197.3, 163.6, 139.1, 136.1,
132.5, 130.8, 130.4, 129.7, 127.9, 125.1, 113.6, 55.5, 19.8. MS: m/z 226
[M]+. Anal. Calcd for C15H14O2: C, 79.62; H, 6.24. Found: C, 79.43;
H, 6.01.
Bis(3,5-bis(trifluoromethyl)phenyl)methanone (3r). Acetophe-
none (0.18 g, 1.5 mmol) and 3,5-bis(trifluoromethyl)bromobenzene
(1.49 g, 5.09 mmol) were used. The product was obtained as a white
solid (0.13 g, 19%). Mp: 144.2−145.2 °C. 1H NMR (400 MHz,
CDCl3, ppm): δ 8.24 (s, 4H), 8.20 (s, 2H). 13C{1H} NMR (100 MHz,
CDCl3, ppm): δ 190.8, 137.6, 133.3, 132.9, 132.6, 132.2, 129.8, 126.8,
124.0, 121.3, 118.6, 109.8. MS: m/z 454 [M]+. Anal. Calcd for
C17H6F12O: C, 44.95; H, 1.33. Found: C, 44.76; H, 1.51.
(3,4-Dimethoxyphenyl)(4-methoxyphenyl)methanone (4e).30
Acetophenone (0.18 g, 1.5 mmol) and 3,4-dimethoxybromobenzene
(0.33 g, 1.5 mmol) and 4-bromoanisole (0.28 g, 1.5 mmol) were used.
The product was obtained as a yellow solid (0.17 g, 41%). Mp: 90.0−
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91.9 °C. H NMR (400 MHz, CDCl3, ppm): δ 7.80 (d, J = 8.7 Hz,
Bis(4-cyanophenyl)methanone (3s).29 Acetophenone (0.18 g, 1.5
mmol) and 4-bromobenzonitrile (0.93 g, 5.09 mmol) were used. The
product was obtained as yellow solid (0.09 g, 26%). Mp: 163.6−164.5
°C. 1H NMR (400 MHz, CDCl3, ppm): δ 7.86 (dd, J1 = 19.1, J2 = 8.2
Hz, 8H). 13C{1H} NMR (100 MHz, CDCl3, ppm): δ 193.4, 139.7,
132.4, 130.2, 117.7, 116.5. MS: m/z 232 [M]+. Anal. Calcd for
C15H8N2O: C, 77.58; H, 3.47; N, 12.06. Found: C, 77.44; H, 3.52; N,
12.25.
2H), 7.44 (d, J = 1.7 Hz, 1H), 7.36 (dd, J = 8.3, 1.7 Hz, 1H), 6.96 (d, J
= 8.7 Hz, 2H), 6.90 (d, J = 8.3 Hz, 1H), 3.96 (s, 3H), 3.94 (s, 3H),
3.88 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, ppm): δ 194.4, 162.7,
152.5, 148.8, 132.1, 130.7, 130.6, 124.7, 113.3, 112.1, 109.6, 55.9, 55.4.
MS: m/z 272 [M]+.
(4-Fluorophenyl)phenylmethanone (4f).14c Acetophenone (0.18 g,
1.5 mmol) and bromobenzene (0.24 g, 1.5 mmol) and 4-
fluorobromobenzene (0.26 g, 1.5 mmol) or 1,2-diphenylethanone
(0.294 g, 1.5 mmol) and 4-fluorobromobenzene (0.26 g, 1.5 mmol)
were used. The product was obtained as a pale yellow oil (0.16 g, 53%;
0.18, 60%). 1H NMR (400 MHz, CDCl3, ppm): δ 7.89−7.74 (m, 4H),
7.59 (ddd, J1 = 7.2, J2 = 2.7, J3 = 1.1 Hz, 1H), 7.53−7.44 (m, 3H), 7.15
(t, J = 8.6 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3, ppm): δ 196.7,
166.6, 164.1, 137.5, 132.6, 132.4, 130.0, 129.8, 128.3, 128.2, 115.5,
115.3. MS: m/z 200 [M]+. Anal. Calcd for C13H9FO: C, 77.99; H,
4.53. Found: C, 78.13; H, 4.42.
Bis(4-carbethoxyphenyl)methanone (3t).29 Acetophenone (0.18 g,
1.5 mmol) and ethyl 4-bromobenzoate (1.16 g, 5.09 mmol) were used.
The product was obtained as a white solid (0.11 g, 22%). Mp: 83.8−
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84.6 °C. H NMR (400 MHz, CDCl3, ppm): δ 8.17 (d, J = 8.4 Hz,
4H), 7.84 (d, J = 8.3 Hz, 4H), 4.43 (q, J = 7.1 Hz, 4H), 1.43 (t, J = 7.1
Hz, 6H). 13C{1H} NMR (100 MHz, CDCl3, ppm): δ 195.3, 165.6,
140.4, 134.0, 129.8, 129.5, 61.5, 14.2. MS: m/z 326 [M]+.
Bis(naphthalen-1-yl)methanone (3u). Acetophenone (0.18 g, 1.5
mmol) and 1-bromonaphthalene (0.62 g, 3.0 mmol) were used. The
product was obtained as a red oil (0.36 g, 86%). 1H NMR (400 MHz,
CDCl3, ppm): δ 8.56 (dd, J1 = 6.5, J2 = 3.0 Hz, 2H), 8.00 (d, J = 8.1
Hz, 2H), 7.92 (dd, J1 = 6.2, J2 = 3.3 Hz, 2H), 7.57 (dt, J1 = 5.8, J2 = 4.4
Hz, 6H), 7.44−7.37 (m, 2H). 13C{1H} NMR (100 MHz, CDCl3,
ppm): δ 199.7, 137.0, 133.8, 132.5, 131.1, 130.4, 128.4, 127.8, 126.5,
125.8, 124.3. MS: m/z 282 [M]+. Anal. Calcd for C21H14O: C, 89.34;
H, 5.00. Found: C, 89.24; H, 4.90.
(3,4-Dimethoxyphenyl)(4-fluorophenyl)methanone (4g).31 Ace-
tophenone (0.18 g, 1.5 mmol) and 3,4-dimethoxybromobenzene (0.33
g, 1.5 mmol) and 4-fluorobromobenzene (0.26 g, 1.5 mmol) were
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used. The product was obtained as a yellow oil (0.15 g, 38%). H
NMR (400 MHz, CDCl3, ppm): δ 7.83−7.78 (m, 2H), 7.48−7.45 (m,
1H), 7.34 (dd, J = 8.3, 1.8 Hz, 1H), 7.15 (t, J = 8.6 Hz, 2H), 6.90 (d, J
= 8.3 Hz, 1H), 3.96 (s, 3H), 3.94 (s, 3H). 13C{1H} NMR (100 MHz,
CDCl3, ppm): δ 194.0, 166.2, 163.6, 152.9, 148.9, 134.3, 132.2, 132.1,
129.9, 129.8, 128.0, 125.1, 115.3, 115.1, 111.9, 109.7, 55.9. MS: m/z
260 [M]+.
(4-Methoxyphenyl)phenylmethanone (4a).12a Acetophenone
(0.18 g, 1.5 mmol) and bromobenzene (0.24 g, 1.5 mmol) and 4-
bromoanisole (0.28 g, 1.5 mmol) or 1,2-diphenylethanone (0.29 4g,
1.5 mmol) and 4-bromoanisole (0.28 g, 1.5 mmol) were used. The
product was obtained as a pale yellow solid (0.11 g, 34%; 0.13, 41%).
(4-Chlorophenyl)(4-methoxyphenyl)methanone (4h).12a Aceto-
phenone (0.18 g, 1.5 mmol) and 4-chlorobromobenzene (0.29 g, 1.5
mmol) and 4-bromoanisole (0.28 g, 1.5 mmol) were used. The
product was obtained as a white solid (0.07 g, 20%). Mp: 114.3−115.1
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Mp: 65.6−66.6 °C. H NMR (400 MHz, CDCl3, ppm): δ 7.85−7.81
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°C. H NMR (400 MHz, CDCl3, ppm): δ 7.79 (d, J = 8.8 Hz, 2H),
(m, 2H), 7.78−7.72 (m, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.46 (t, J = 7.7
Hz, 2H), 6.96 (d, J = 8.8 Hz, 2H). 13C{1H} NMR (100 MHz, CDCl3,
ppm): δ 195.5, 163.1, 138.1, 132.5, 131.8, 130.0, 129.6, 128.1, 113.4,
55.4. MS: m/z 212 [M]+. Anal. Calcd for C14H12O2: C, 79.22; H, 5.70.
Found: C, 79.02; H, 5.52.
7.70 (d, J = 8.4 Hz, 2H), 7.45 (d, J = 8.4 Hz, 2H), 6.96 (d, J = 8.7 Hz,
2H), 3.88 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, ppm): δ 194.2,
163.3, 138.2, 136.5, 132.4, 131.1, 129.7, 128.5, 113.6, 55.5. MS: m/z
246[M]+.
(4-Fluorophenyl)(4-methoxyphenyl)methanone (4i).14a Aceto-
phenone (0.18 g, 1.5 mmol) and 4-fluorobromobenzene (0.26 g, 1.5
mmol) and 4-bromoanisole (0.28 g, 1.5 mmol) were used. The
product was obtained as a white solid (0.11 g, 32%). Mp: 92.9−93.8
(4-Methoxyphenyl)-p-tolylmethanone (4b).14a Acetophenone
(0.18 g, 1.5 mmol) and 4-bromotoluene (0.26 g, 1.5 mmol) and 4-
bromoanisole (0.28 g, 1.5 mmol) were used. The product was
obtained as a white solid (0.18 g, 53%). Mp: 91.5−92.2 °C. 1H NMR
(400 MHz, CDCl3, ppm): δ 7.81 (d, J = 8.0 Hz, 2H), 7.67 (d, J = 8.1
Hz, 2H), 7.29−7.24 (m, 2H), 6.95 (d, J = 8.0 Hz, 2H), 3.87 (s, 3H),
2.43 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, ppm): δ 195.3, 162.9,
142.6, 135.4, 132.4, 130.3, 130.0, 128.8, 113.4, 55.4, 21.6. MS: m/z 226
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°C. H NMR (400 MHz, CDCl3, ppm): δ 7.80 (dt, J1 = 8.8, J2 = 2.7
Hz, 4H), 7.16 (t, J = 8.6 Hz, 2H), 7.03−6.89 (m, 2H), 3.90 (s, 3H).
13C{1H} NMR (100 MHz, CDCl3, ppm): δ 194.1, 166.2, 163.7, 163.2,
134.4, 132.5, 132.4, 132.3, 132.2, 129.9, 129.7, 128.1, 115.4, 115.2,
G
dx.doi.org/10.1021/jo5010185 | J. Org. Chem. XXXX, XXX, XXX−XXX