The Journal of Organic Chemistry
Note
1-(4-(2-Phenylallyl)phenyl)ethan-1-one (6b). From 57 mg (0.25
mmol, 0.05 M) of 1b and 680 mg (2.5 mmol, 0.5 M) of 3 in MeCN−
H2O 9:1 (5 mL). Purification by column chromatography (eluant:
pentane/diethyl ether 8:2) afforded 56 mg of 6b (pale yellow oil, 95%
yield). The spectroscopic data of 6b were in accordance with the
literature.40
1-Chloro-4-(2-phenylallyl)benzene (6c). From 54.3 mg (0.25 mmol,
0.05 M) of 1c and 680 mg (2.5 mmol, 0.5 M) of 3 in MeCN−H2O 9:1 (5
mL). Purification by column chromatography (eluant: pentane)
afforded 33 mg of 6c (colorless oil, 58% yield). The spectroscopic
data of 6c were in accordance with the literature.40
1-Bromo-4-(2-phenylallyl)benzene (6d). From 67.5 mg (0.25 mmol,
0.05 M) of 1d and 680 mg (2.5 mmol, 0.5 M) of 3 in MeCN−H2O 9:1
(5 mL). Purification by column chromatography (eluant: pentane)
afforded 39.5 mg of 6d (pale yellow oil, 58% yield). The spectroscopic
data of 6d were in accordance with the literature.41
Prop-2-ene-1,2-diyldibenzene (6e). From 46 mg (0.25 mmol, 0.05
M) of 1e and 680 mg (2.5 mmol, 0.5 M) of 3 in MeCN−H2O 9:1 (5
mL). Purification by column chromatography (eluant: pentane)
afforded 35 mg of 6e (colorless oil, 72% yield). The spectroscopic
data of 6e were in accordance with the literature.42
1-(tert-Butyl)-4-(2-phenylallyl)benzene (6f). From 60 mg (0.25
mmol, 0.05 M) of 1f and 680 mg (2.5 mmol, 0.5 M) of 3 in MeCN−
H2O 9:1 (5 mL). Purification by column chromatography (eluant:
pentane) afforded 30.5 mg of 6f (pale yellow oil, 49% yield) along with
462 mg of 3 (75% of the unreacted material recovered) that were
isolated by column chromatography. 1H NMR (300 MHz,
CD3COCD3) δ 7.51−7.54 (m, 2H), 7.18−7.33 (m, 7H), 5.52 (s,
1H), 5.10 (s, 1H), 3.86 (s, 2H), 1.28 (s, 9H). 13C NMR (75 MHz,
CD3COCD3) δ 149.8, 148.6, 141.9, 137.8, 129.7 (CH), 129.5 (CH),
128.7 (CH), 127.4 (CH), 126.3 (CH), 115.0 (CH2), 41.8 (CH2), 35.2,
32.1 (CH3). IR (NaCl, ν cm−1): 2963, 2866, 1515, 898. GC-MS (m/z):
250 (M+, 5), 236 (9), 235 (48), 194 (28), 193 (100), 192 (52), 117 (38),
115 (47). Anal. Calcd for C19H22 C, 91.1; H, 8.9. Found: C, 90.8; H, 9.0.
3-(2-Phenylallyl)benzonitrile (6g). From 51 mg (0.25 mmol, 0.05
M) of 1g and 680 mg (2.5 mmol, 0.5 M) of 4 in MeCN−H2O 9:1 (5
mL). Purification by column chromatography (eluant: pentane/diethyl
ether 8:2) afforded 38 mg of 6g (pale yellow oil, 70% yield). 1H NMR
(300 MHz, CD3COCD3) δ 7.66−7.48 (m, 5H), 7.34−7.24 (m, 4H),
5.57 (s, 1H), 5.17 (s, 1H), 4.01 (s, 2H). 13C NMR (75 MHz,
CD3COCD3) δ: 147.7, 142.8, 141.2, 134.8, 133.5 (CH), 131.1 (CH),
130.6 (CH), 129.6 (CH), 128.9 (CH), 127.4 (CH), 119.8 (CH), 115.9
(CH2), 113.4, 41.7 (CH2). IR (NaCl, ν cm−1): 2229, 1627, 1600, 1582.
GC-MS (m/z): 219 (M+, 17), 204 (6), 141 (24), 103 (100). Anal. Calcd
for C16H13N: C, 87.6; H, 6.0; N, 6.4. Found C, 87.8; H, 5.9; N, 6.3.
2-(2-Phenylallyl)benzonitrile (6h). From 51 mg (0.25 mmol, 0.05
M) of 1h and 680 mg (2.5 mmol, 0.5 M) of 4 in MeCN−H2O 9:1 (5
mL). Purification by column chromatography (eluant: pentane/diethyl
ether 8:2) afforded 19 mg of 6h (colorless oil, 35% yield). 1H NMR (300
MHz, CD3COCD3) δ 7.77−7.60 (m, 1H), 7.55−7.29 (m, 8H), 5.54 (s,
1H), 4.99 (s, 1H), 4.11 (s, 2H). 13C NMR (75 MHz, CD3COCD3) δ:
35.4 (CH2), 109.0, 113.7 (CH2), 113.6, 122.1 (CH), 123.2 (CH), 123.8
(CH), 124.4 (CH), 126.3 (CH), 128.8 (CH), 136.3, 139.2, 142.1, 36.4
(CH3). IR (NaCl, ν cm−1): 2924, 2218, 1488, 1441, 901. GC-MS (m/z):
219 (M+, 22), 218 (10), 141 (12), 117 (14), 103 (100). Anal. Calcd for
C16H13N: C, 87.6; H, 6.0; N, 6.4. Found C, 87.4; H, 5.8; N 6.5
2,3-Difluoro-3-(2-phenylallyl)benzene (6i). From 55 mg (0.25
mmol, 0.05 M) of 1i and 680 mg (2.5 mmol, 5 M) of 4 in MeCN−
H2O 9:1 (5 mL). Purification by column chromatography (eluant:
pentane/diethyl ether 95:5) afforded 22 mg of 6i (colorless oil, 38%
yield). 1H NMR (300 MHz, CD3COCD3) δ 7.54−7.51 (m, 2H), 7.37−
7.28 (m, 3H), 7.12−7.08 (m, 3H), 5.53 (s, 1H), 5.05 (s, 1H), 3.96 (s,
2H). 13C NMR (75 MHz, CD3COCD3) δ: 152.0 (dd, J = 120 and 12.7
Hz), 150.0 (d, J = 134 Hz), 146.9, 141.4, 130.4 (d, J = 12.7 Hz), 129.6
(CH), 129.0 (CH), 127.4 (t, J = 12.7 Hz), 125.5 (m, CH), 116.4 (CH, J
= 75 Hz), 115.3 (CH), 134.7 (CH2) 34.7 (CH3). IR (NaCl, ν cm−1):
2921, 2847, 901. GC-MS (m/z): 230 (19), 210 (5), 152 (28), 103 (100),
77 (25). Anal. Calcd for C15H12F2: C, 78.2; H, 5.2. Found C, 78.1; H, 5.1.
2-(2-Phenylallyl)naphthalene (6j). From 58.5 mg (0.25 mmol, 0.05
M) of 1j and 680 mg (2.5 mmol, 5 M) of 4 in MeCN−H2O 9:1 (5 mL).
Purification by column chromatography (eluant: neat pentane) afforded
33.5 mg of 6j (pale yellow oil, 55% yield). The spectroscopic data of 6j
were in accordance with the literature.42
Methyl 2-(4-Cyanobenzyl)acrylate (7a). From 51 mg (0.25 mmol,
0.05 M) of 1a and 636 mg of methyl 2-(tosylmethyl)acrylate (4a, 2.5
mmol, 0.5 M) in MeCN−H2O 9:1 (5 mL). Purification by column
chromatography (eluant: pentane/diethyl ether 9:1) afforded 36 mg of
7a43 (pale yellow oil, 72% yield).
1H NMR (300 MHz, CDCl3) δ: 7.62−7.59 (d, 2H, J = 9 Hz) 7.35−
7.32 (d, 2H, J = 9 Hz), 6.31 (s, 1H), 5.57 (s, 1H), 3.74 (s, 3H), 3.70 (s,
2H). 13C NMR (75 MHz, CDCl3) δ: 144.4, 138.6, 132.1 (CH), 129.6
(CH), 127.2 (CH2), 118.8, 110.3, 52.0 (CH2), 38.2 (CH3). IR (NaCl, ν
cm−1): 2230, 1719, 1632. ESI-MS (m/z): 202.2 (M+ + H+). Anal. Calcd
for C12H11NO2: C, 71.6; H, 5.5; N, 7.0. Found: C, 71.8; H, 5.7; N, 6.8.
Methyl 2-(4-Acetylbenzyl)acrylate (7b). From 57 mg (0.25 mmol,
0.05 M) of 7b and 635 mg (2.5 mmol, 0.5 M) of 4a in MeCN−H2O 9:1
(5 mL). Purification by column chromatography (eluant: pentane/
diethyl ether 9:1) afforded 51 mg of 7b (yellow oil, 93% yield) along
with 419 mg of 4a (73% of the unreacted material recovered) were
1
isolated by column chromatography. H NMR (300 MHz, CDCl3) δ:
7.93−7.90 (d, 2H, J = 9 Hz) 7.33−7.30 (d, 2H, J = 9 Hz), 6.29 (s, 1H),
5.54 (s, 1H), 3.75 (s, 3H), 3.70 (s, 2H), 2.60 (s, 3H). 13C NMR (75
MHz, CDCl3) δ: 197.7, 166.9, 144.4, 139.3, 135.4, 129.0 (CH), 128.5
(CH), 126.8 (CH2), 51.9 (CH2), 38.0 (CH3), 26.5 (CH3). IR (NaCl, ν
cm−1): 1720, 1640. GC-MS (m/z): 218 (M+, 28), 203 (66), 158 (16),
143 (100). Anal. Calcd for C13H14O3: C, 71.5; H, 6.5. Found: C, 71.4; H,
6.4.
Methyl 2-(4-Chlorobenzyl)acrylate (7c). From 54.3 mg (0.25 mmol,
0.05 M) of 1c and 635 mg (2.5 mmol, 5 M) of 4a in MeCN−H2O 9:1 (5
mL). Purification by column chromatography (eluant: pentane/diethyl
ether 9:1) afforded 25 mg of 7c (colorless oil, 47% yield). The
spectroscopic data of 7c were in accordance with the literature.44 The
same reaction carried out by using allyl methylsulfone 4b instead of 4a
afforded 7c in 53% yield.
Methyl 2-(4-Bromobenzyl)acrylate (7d). From 67.5 mg (0.25 mmol,
0.05 M) of 1d and 635 mg (2.5 mmol, 0.5 M) of 4a in MeCN−H2O 9:1
(5 mL). Purification by column chromatography (eluant: pentane/
diethyl ether 9:1) afforded 20 mg of 7d (yellow oil, 31% yield). The
spectroscopic data of 7d were in accordance with the literature.44 The
same reaction carried out by using 4b instead of 4a afforded 7d in 39%
yield.
Methyl 2-(3-Cyanobenzyl)acrylate (7g). From 52 mg (0.25 mmol,
0.05 M) of 1g and 635 mg (2.5 mmol, 0.5 M) of 4a in MeCN−H2O 9:1
(5 mL). Purification by column chromatography (eluant: pentane)
afforded 38.2 mg of 7g (colorless oil, 76% yield). Spectroscopic data of
7g were in accordance with the literature.45
Methyl 2-(4-Nitrobenzyl)acrylate (7k). From 57 mg (0.25 mmol,
0.05 M) of 1k and 635 mg (2.5 mmol, 0.5 M) of 4a in MeCN−H2O 9:1
(5 mL). Purification by column chromatography (eluant: pentane/
diethyl ether 9:1) afforded 27.6 mg of 7k46 (yellow oil, 50% yield). 1H
NMR (300 MHz, CD3COCD3) δ: 8.20−8.17 (d, 2H, J = 9 Hz), 7.56−
7.53 (d, 2H, J = 9 Hz), 6.28 (s, 1H), 5.76 (s, 1H), 3.81 (s, 2H), 3.70 (s,
3H). 13C NMR (75 MHz, CD3COCD3) δ: 167.6, 148.6, 140.4, 131,2
(CH), 128.1 (CH), 124.7 (CH2), 52.6 (CH2), 38.8 (CH3). IR (NaCl, ν
cm−1): 1721, 1519, 1633. GC-MS (m/z): 221 (M+, 16), 204 (30), 174
(18), 161 (62), 116 (57), 115 (100). Anal. Calcd for C11H11NO4: C,
59.7; H, 5.0; N, 6.3. Found: 59.5, H; 4.9, N, 6.4.
Methyl 2-(4-Methylbenzyl)acrylate (7l). From 50 mg (0.25 mmol,
0.05 M) of 1l and 635 mg (2.5 mmol, 0.5 M) of 4a in MeCN−H2O 9:1
(5 mL). Purification by column chromatography (eluant: pentane/
diethyl ether 9:1) afforded 23 mg of 7l (colorless oil, 48% yield). The
spectroscopic data of 7l were in accordance with the literature.44
Methyl 2-(4-Methoxybenzyl)acrylate (7m). From 53.5 mg (0.25
mmol, 0.05 M) of 1m and 635 mg (2.5 mmol, 0.5 M) of 4a in MeCN−
H2O 9:1 (5 mL). Purification by column chromatography (eluant:
pentane/diethyl ether 9:1) afforded 20 mg of 7m (colorless oil, 39%
yield). The spectroscopic data of 7m were in accordance with the
literature.47
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J. Org. Chem. XXXX, XXX, XXX−XXX