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127.5, 127.0, 126.0, 125.5, 125.3, 124.6, 124.0, 73.5. Found (%):
C, 87.02; H, 6.16. Calculated (%): C, 87.15; H, 6.02.
J = 3.6 Hz); 7.61 (t, 1 H, J = 7.4 Hz); 7.51 (t, 2 H, J = 7.8 Hz);
7.17 (t, 1 H, J = 4.4 Hz). 13C NMR (CDCl3), δ: 188.2, 143.6,
138.1, 134.8, 134.1, 132.2, 129.1, 128.3, 127.9. Found (%):
C, 70.39; H, 4.05. Calculated (%): C 70.18; H, 4.28.
(3ꢀMethylꢀ2ꢀthienyl)(phenyl)methanone (4al). 1H NMR
(CDCl3), δ: 7.78—7.75 (m, 2 H); 7.70—7.66 (m, 1 H); 7.46—
7.41 (m, 2 H); 7.32 (d, 1 H, J = 7.3 Hz); 6.86—6.84 (d, 1 H, J =
= 7.3 Hz); 2.20 (s, 3 H). Found (%): C, 71.14; H, 5.20. Calculatꢀ
ed (%): C, 71.25; H, 4.98.
(Phenyl)(oꢀtolyl)methanone (4ba). 1H NMR (CDCl3), δ: 7.78
(d, 2 H, J = 8.4 Hz); 7.55—7.62 (m, 1 H); 7.24—7.49 (m, 6 H);
2.32 (s, 3 H). 13C NMR (CDCl3), δ: 198.5, 138.5, 137.7, 136.8,
133.0, 130.9, 130.1, 130.0, 128.4, 128.3, 125.1, 19.9. Found (%):
C, 85.49; H, 6.06. Calculated (%): C, 85.68; H, 6.16.
(Biphenylꢀ2ꢀyl)(phenyl)methanone (4da). 1H NMR (CDCl3),
δ: 7.64 (d, 2 H, J = 7.9 Hz); 7.57—7.56 (m, 1 H); 7.52—7.38
(m, 4 H); 7.28—7.25 (m, 4 H); 7.21—7.14 (m, 3 H). 13C NMR
(CDCl3), δ: 198.74, 141.11, 140.13, 138.93, 137.35, 132.76,
130.32, 130.02, 129.86, 128.96, 128.73, 128.20, 128.03, 127.28,
127.02. Found (%): C, 88.50; H, 5.33. Calculated (%): C, 88.34;
H, 5.46.
(4ꢀFluorophenyl)(phenyl)methanone (4fa). 1H NMR
(CDCl3), δ: 7.72—7.68 (m, 2 H); 7.64—7.62 (m, 2 H); 7.46—
7.42 (m, 1 H); 7.35—7.32 (t, 2 H, J = 7.3 Hz); 7.02—6.98 (t, 2 H,
J = 7.0 Hz). 13C NMR (CDCl3), δ: 194.0, 165.5, 163.0, 136.4,
132.7, 132.7, 131.6, 131.5, 131.4, 128.8, 127.3, 114.5, 114.3.
Found (%): C, 77.82; H, 4.55. Calculated (%): C, 77.99; H, 4.53.
(Phenyl)(3ꢀtrifluoromethylphenyl)methanone (4ga). 1H NMR
(CDCl3), δ: 7.91—7.89 (d, 2 H, J = 7.9 Hz); 7.82—7.80 (m, 2 H);
7.77—7.75 (d, 2 H, J = 7.8 Hz); 7.65—7.62 (t, 1 H, J = 7.6 Hz);
7.53—7.49 (t, 2 H, J = 7.5 Hz). 13C NMR (CDCl3), δ: 195.6,
140.7, 136.7, 133.9, 133.6, 133.1, 130.6, 130.2, 130.1, 128.5,
125.4, 125.3, 125.0, 122.3. Found (%): C, 67.04; H, 3.45. Calcuꢀ
lated (%): C, 67.20; H, 3.63.
(4ꢀMethoxyphenyl)(phenyl)methanone (4ha). 1H NMR
(CDCl3), δ: 7.84 (d, 2 H, J = 8.8 Hz); 7.74—7.76 (m, 2 H); 7.55
(d, 1 H, J = 7.5 Hz); 7.46 (t, 2 H, J = 7.6 Hz); 6.96 (d, 2 H,
J = 8.8 Hz); 3.87 (s, 3 H). 13C NMR (CDCl3), δ: 195.4, 163.3,
138.4, 132.5, 131.8, 130.1, 129.6, 128.1, 113.5, 55.4. Found (%):
C, 79.39; H, 5.81. Calculated (%): C, 79.22; H, 5.70.
1,4ꢀPhenylenebis(phenylmethanone) (4ka). 1H NMR
(CDCl3), δ: 7.48—7.54 (m, 4 H); 7.60—7.65 (m, 2 H); 7.82—
7.86 (m, 4 H); 7.88 (s, 4 H). 13C NMR (CDCl3), δ: 196.1, 140.8,
137.1, 133.1, 130.2, 129.8, 128.6. Found (%): C, 84.06; H, 5.11.
Calculated (%): C, 83.90; H, 4.93.
(1ꢀNaphthyl)(phenyl)methanone (4na). 1H NMR (CDCl3),
δ: 8.10 (d, 1 H, J = 8.0 Hz); 8.00 (d, 1 H, J = 8.4 Hz); 7.93 (t, 1 H,
J = 4.8 Hz); 7.87—7.89 (m, 2 H); 7.56—7.63 (m, 2 H); 7.51—
7.55 (m, 3 H); 7.45—7.51 (m, 2 H). 13C NMR (CDCl3), δ:
198.0, 138.3, 136.3, 133.7, 133.3, 131.2, 131.0, 130.4, 128.5,
128.4, 127.7, 127.2, 126.5, 125.8, 124.3. Found (%): C, 87.68;
H, 5.08. Calculated (%): C, 87.90; H, 5.21.
(1,3ꢀBenzodioxolꢀ5ꢀyl)(phenyl)methanol (3oa). 1H NMR
(CDCl3), δ: 7.26—7.14 (m, 5 H); 6.75—6.64 (m, 3 H); 5.80 (s, 2 H);
5.62 (s, 1 H); 2.30 (s, 1 H). 13C NMR (CDCl3), δ: 148.18,
147.37, 144.19, 140.26, 138.39, 128.89, 127.88, 126.73, 120.38,
108.47, 107.56, 101.41, 76.35. Found (%): C, 73.53; H, 5.39.
Calculated (%): C, 73.67; H, 5.30.
(Phenyl)(3ꢀthienyl)methanol (3pa). 1H NMR (CDCl3), δ:
7.42—7.26 (m, 6 H); 7.19—7.18 (m, 1 H); 7.01—6.99 (m, 1 H);
5.88 (s, 1 H); 2.34 (s, 1 H). 13C NMR (CDCl3), δ: 145.26,
143.31, 128.46, 127.71, 126.44, 126.35, 126.14, 121.61, 72.75.
Found (%): C, 69.24; H, 5.39. Calculated (%): C, 69.44; H, 5.30.
(Phenyl)(pꢀtolyl)methanol (3ra). 1H NMR (CDCl3), δ: 7.39–
7.28 (m, 5 H); 7.26 (d, 2 H, J = 8.0 Hz); 7.15 (d, 2 H, J = 8.0 Hz);
5.99 (s, 1 H); 2.36 (s, 3 H); 2.18 (br.s, 1 H). 13C NMR (CDCl3),
δ: 143.9, 140.9, 137.4, 129.3, 128.4, 127.5, 126.6, 126.4, 76.2,
21.2. Found (%): C, 84.70; H, 7.33. Calculated (%): C, 84.81;
H, 7.12.
Synthesis of benzophenones by the coupling reaction of aryl
halides and benzaldehydes (general procedure). Activated zinc
(75 mg, 1.15 mmol), LiCl (21.3 mg, 0.05 mmol), NiBr2(DME)
(15.4 mg, 0.05 mmol), and ligand L4 (0.05 mmol) were placed
into a 8ꢀmL glass vial using an atmosphereꢀcontrolled glove box.
Then, 0.2 M solution of benzaldehyde (5 mL, 1 mmol) in THF
and aryl halide (1.15 mmol) were added to this mixture. The
reaction mixture was magnetically stirred at 70 °C, the target
product was isolated from the reaction mixture by column chroꢀ
matography on silica gel 60 Å (40—60 mesh).
Benzophenone (4aa). 1H NMR (CDCl3), δ: 7.47—7.50
(m, 4 H); 7.58—7.61 (m, 2 H); 7.81 (d, 4 H, J = 7.5 Hz). 13C
NMR (CDCl3), δ: 196.9, 137.8, 132.5, 130.2, 128.4. Found (%):
C, 88.70; H, 5.31. Calculated (%): C, 85.69; H, 5.53.
(3ꢀFluorophenyl)(phenyl)methanone (4ac). 1H NMR
(CDCl3), δ: 7.88—7.73 (m, 2 H); 7.69—7.55 (m, 2 H); 7.55—
7.37 (m, 4 H); 7.29 (tdd, 1 H, J = 8.3 Hz, J = 2.6 Hz, J = 1.1 Hz).
13C NMR (CDCl3), δ: 195.37, 162.55, 139.71, 137.08, 132.88,
130.10, 130.05, 128.51, 125.92, 119.51, 116.81. Found (%):
C, 77.73; H, 4.69. Calculated (%): C, 77.99; H, 4.53.
(3ꢀMethoxyphenyl)(phenyl)methanone (4ad). 1H NMR
(CDCl3), δ: 7.81 (dd, 2 H, J = 1.3 Hz, J = 8.5 Hz); 7.57—7.60
(m, 1 H); 7.48 (dd, 2 H, J = 7.6 Hz, J = 7.8 Hz); 7.33—7.39
(m, 3 H); 7.12—7.15 (m, 1 H); 3.86 (s, 3 H). 13C NMR (CDCl3), δ:
196.5 159.6 138.9, 137.6, 132.4, 130.1, 129.2, 128.3, 122.9, 118.9,
114.3, 55.5. Found (%): C, 79.01; H, 5.61. Calculated (%):
C, 79.22; H, 5.70.
(Phenyl)(2,4,5ꢀtrimethoxyphenyl)methanone (4af). 1H NMR
(CDCl3), δ: 7.77 (dd, 2 H, J = 8.0 Hz, J = 1.6 Hz); 7.52 (tt, 1 H,
J = 7.4 Hz, J = 1.4 Hz); 7.41 (t, 2 H, J = 8.0 Hz); 7.04 (s, 1 H);
6.57 (s, 1 H); 3.95 (s, 3 H); 3.84 (s, 3 H); 3.65 (s, 3 H). 13C NMR
(CDCl3), δ: 195.37, 153.17, 152.40, 142.91, 138.73, 132.15,
129.31, 127.81, 119.61, 113.25, 97.28, 56.34, 56.27, 55.94.
Found (%): C, 70.39; H, 5.78. Calculated (%): C, 70.57; H, 5.92.
(4ꢀDimethylaminophenyl)(phenyl)methanone (4ah). 1H NMR
(CDCl3), δ: 7.83 (d, 2 H, J = 8.6 Hz); 7.69 (d, 2 H, J = 7.6 Hz);
7.28 (d, 2 H, J = 7.1 Hz); 6.70 (d, 2 H, J = 8.5 Hz); 3.09 (s, 6 H);
2.46 (s, 3 H). 13C NMR (CDCl3), δ: 194.7, 153.0, 141.5, 136.3,
132.4, 129.5, 128.5, 124.9, 110.4, 39.8, 21.4. Found (%): C, 79.78;
H, 6.96; N, 6.02. Calculated (%): C, 79.97; H, 6.71; N, 6.22.
(Phenyl)(2ꢀthienyl)methanone (4ak). 1H NMR (CDCl3), δ:
7.87 (d, 2 H, J = 7.6 Hz); 7.73 (d, 1 H, J = 4.8 Hz); 7.65 (d, 1 H,
(Phenyl)(3ꢀthienyl)methanone (4pa). 1H NMR (CDCl3), δ:
7.88—7.84 (m, 2 H); 7.68—7.58 (m, 2 H); 7.51—7.46 (m, 2 H);
7.38 (d, 1 H, J = 3.3 Hz). 13C NMR (CDCl3), δ: 189.79, 139.21,
137.44, 133.25, 132.26, 130.05, 128.46, 125.08, 110.56. Found
(%): C, 70.35; H, 4.19. Calculated (%): C, 70.18; H, 4.28.
(Phenyl)(pꢀtolyl)methanone (4ra). 1H NMR (CDCl3), δ:
7.77—7.79 (m, 2 H); 7.72 (d, 2 H, J = 8.1 Hz); 7.56 (t, 1 H,
J = 7.5 Hz); 7.44 (t, 2 H, J = 7.5 Hz); 7.27 (d, 2 H, J = 8.1 Hz);
2.44 (s, 3 H). 13C NMR (CDCl3), δ: 196.5, 143.2, 137.9, 134.9,