Nikitin and Andryukhova
575
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for 16 h, cooled, the organic layer was separated, washed
with aq. NaOH, water, then dried (MgSO4), evaported under
reduced pressure, and subjected to column chtomatography
separation (20% ethyl acetate – hexane) to afford 2-(2-
bromoethoxy)-acetophenone (6a) (1.86 g, 65% yield) as a
solid; mp 69 °C. H NMR (200 MHz, CDCl3) δ: 2.65 (s,
3H), 3.72 (t, 2H, J = 5.8 Hz), 3.85 (s, 3H), 4.38 (t, 2H, J =
5.8 Hz), 6.39 (d, 1H, J = 2.2 Hz), 6.46 (dd, 1H, J = 2.2 Hz,
J = 8.8 Hz), 7.87 (d, 1H, J = 8.8 Hz). MS (70 eV) m/z: 272,
274 (M + 2).
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colorless solid; mp 45 °C. H NMR (200 MHz, CDCl3) δ:
2-(2-Bromoethoxy)-acetonaphthone (6e) (1.0 g, 63% yield)
was obtained from 2-hydroxyacetonaphthone (1.0 g) and
1,2-dibromoethane (11 g) as a colorless solid; mp 89 °C. H
NMR (200 MHz, CDCl3) δ: 2.72 (s, 3H), 3.68 (t, 2H, J =
6 Hz), 4.48 (t, 2H, J = 6 Hz), 7.2–7.9 (m, 6H). MS (70 eV)
m/z: 292, 294 (M + 2).
2.68 (s, 3H), 3.70 (t, 2H, J = 5.8 Hz), 4.39 (t, 2H, J =
5.8 Hz), 6.8–7.8 (m, 4H). MS (70 eV) m/z: 242, 244 (M +
2); and 1,2-bis(2-acetylphenoxy)-ethane (13a) (0.31 g, 20%
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yield) as colorless solid; mp 125 °C. H NMR (200 MHz,
CDCl3) δ: 2.59 (s, 6H), 4.50 (s, 4H), 6.9–7.1 (m, 4H), 7.5
(m, 2H), 7.7–7.8 (m, 2H). MS (70 eV) m/z: 298.
2-(2-Chloroethoxy)-propiophenone (6f) (1.32 g, 64% yield)
2-(3-Bromopropoxy)-acetophenone (7a) (1.5 g, 52% yield)
was obtained from 2-hydroxyacetophenone (1.36 g) and 1,3-
dibromopropane (7g) as a colorless liquid. 1H NMR
(200 MHz, CDCl3) δ: 2.37 (tt, 2H, J1 = J2 = 6.3 Hz), 2.59 (s,
3H), 3.61 (t, 2H, J = 6.3 Hz), 4.22 (t, 2H, J = 6.3 Hz), 6.9–
7.8 (m, 4H). MS (70 eV) m/z: 286, 288 (M + 2); along with
1,3-bis(2-acetylphenoxy)-propane (14a) (0.30 g, 18% yield)
was obtained from 2-hydroxypropiophenone (1.5 g) and 1,2-
dichloroethane (15 g) as a colorless solid; mp 56 °C. H
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NMR (200 MHz, CDCl3) δ: 1.17 (t, 3H, J = 7.2 Hz), 3.05 (t,
2H, J = 7.2 Hz), 3.86 (t, 2H, J = 5.5 Hz), 4.32 (t, 2H, J =
5.5 Hz), 6.8–7.1 (m, 2H), 7.4 (m, 1H), 7.7 (m, 1H). MS
(70 eV) m/z: 212; along with 13c (0.22 g, 14% yield).
Pyrrolones 9a–9i, 15, and 17 were prepared via the stan-
dard procedure including reduction of maleimides (17, 18).
1-(α,α-Dimethyl-3,5-dichlorobenzyl)-3-(2-fluorophenyl)-4-
methyl-5-(2-chloroethoxy)-(2,5)-dihydro-2-pyrrolone (9a) as
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as colorless solid; mp 107 °C. H NMR (200 MHz, CDCl3)
δ: 2.42 (quintet, 2H, J = 6.1 Hz), 2.62 (s, 6H), 4.30 (t, 4H,
J = 6.1 Hz), 6.9–7.1 (m, 4H), 7.4–7.5 (m, 2H), 7.7–7.8 (m,
2H). MS (70 eV) m/z: 313 (M + 1).
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a colorless oil. H NMR (200 MHz, CDCl3) δ: 1.79 (s, 3H),
2-(4-Bromobutoxy)-acetophenone (8a) (1.0 g, 33% yield)
1.88 (s, 3H), 2.04 (s, 3H), 3.4–3.7 (m, 4H), 5.75 s (s, 1H),
7.0–7.4 (m, 7H).
was obtained from 2-hydroxyacetophenone (1.36 g) and 1,4-
dibromobutane (8g) as
a
colorless liquid. 1H NMR
1-Phenyl-3,4-dimethyl-5-(2-chloroethoxy)-(2,5)-dihydro-
2-pyrrolone (9b) as a colorless oil. 1H NMR (200 MHz,
CDCl3) δ: 1.90 (s, 3H), 2.03 (s, 3H), 3.2–3.5 (m, 4H), 5.79
(s, 1H), 7.1–7.8 (m, 5H).
1-Isopropyl-3,4-dimethyl-5-(2-chloroethoxy)-(2,5) dihy-
dro-2-pyrrolone (9c) was obtained as a colorless oil. 1H
NMR (200 MHz, CDCl3) δ: 1.22 (d, 6H, J = 7 Hz), 1.72 (s,
3H), 184 (s, 3H), 3.15 (m, 1H), 3.5 (m, 3H), 4.11 (m, 1H),
5.23 (s, 1H).
(200 MHz, CDCl3) δ: 1.9–2.2 (m, 4H), 2.62 (s, 3H), 3.49 (t,
2H, J = 5.8 Hz), 4.10 (t, 2H, J = 5.8 Hz), 6.9–7.1 (m, 2H),
7.4–7.5 (m, 1H), 7.7–7.8 (m, 1H). MS (70 eV) m/z: 300, 302
(M + 2).
2-Bromomethoxy-acetophenone (5a) was not obtained
from 2-hydroxyacetophenone (1.36 g) and dibromomethane
(7g) but only 1,1-bis(2-acetylphenoxy)-methane (12a) (1 g,
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70% yield) was obtained as colorless solid; mp 97 °C. H
NMR (200 MHz, CDCl3) δ: 2.59 (s, 6H), 5.93 (s, 2H), 7.0–
7.75 (m, 8H). MS (70 eV) m/z: 149 (M – AcC6H4O).
2-(2-Bromoethoxy)-5-methylacetophenone (6b) (1.6 g,
62% yield) was obtained from 2-hydroxy-5-methylaceto-
phenone (1.5 g) and 1,2-dibromoethane (11g) as a colorless
1-tert-Butyl-3,4-dimethyl-5-(2-chloroethoxy)-(2,5)-dihydro-
2-pyrrolone (9d) was obtained as a colorless oil. H NMR
(200 MHz, CDCl3) δ: 1.47 (s, 9H), 1.76 (s, 3H), 1.88 (s,
3H), 3.2 (m, 1H), 3.6 (m, 3H), 5.37 (s, 1H).
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1-(2-Fluoro-4-chloro-5-hydroxyphenyl)-3,4-dimethyl-5-
(2-chloroethoxy)-(2,5)-dihydro-2-pyrrolone (9e) was ob-
tained as a solid; mp 148 °C. 1H NMR (200 MHz, CDCl3) δ:
1.92 (s, 3H), 2.05 (s, 3H), 3.3–3.7 (m, 4H), 5.75 (s, 1H),
6.79 (s, 1H), 7.0–7.3 (m, 2H).
1-(2-Fluoro-4-chloro-5-hydroxyphenyl)-3,4-dimethyl-5-
(2-bromoethoxy)-(2,5)-dihydro-2-pyrrolone (9f) was ob-
tained as a solid; mp 149 °C. 1H NMR (200 MHz, CDCl3) δ:
1.90 (s, 3H), 2.05 (s, 3H), 3.3–3.7 (m, 4H), 5.74 (s, 1H),
6.9–7.3 (m, 2H).
1-Benzyl-4-methyl-5-(2-chloroethoxy)-(2,5)-dihydro-2-
pyrrolone (9g) was obtained as a colorless oil. 1H NMR
(200 MHz, CDCl3) δ: 1.92 (s, 3H), 3.2–3.5 (m, 4H), 4.12 (d,
1H, J = 15 Hz), 4.8 (d, 1H, J = 15 Hz), 5.06 (s, 1H), 5.89 (s,
1H), 7.25 (s, 5H).
1-Benzyl-3,4-dimethyl-5-(2-chloroethoxy)-(2,5)-dihydro-
2-pyrrolone (9h) as a colorless oil. 1H NMR (200 MHz,
CDCl3) δ: 1.80 (s, 3H), 1.83 (s, 3H), 3.1–3.5 (m, 4H), 4.17
(d, 1H, J = 15 Hz), 4.83 (d, 1H, J = 15 Hz), 4.99 (s, 1H),
7.25 (s, 5H).
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solid; mp 66 °C. H NMR (200 MHz, CDCl3) δ: 2.30 (s,
3H), 2.67 (s, 3H), 3.70 (t, 2H, J = 5.8 Hz), 4.38 (t, 2H, J =
5.8 Hz), 6.8–7.1 (m, 2H), 7.4 (m, 1H), 7.7 (m, 1H). MS
(70 eV) m/z: 256, 258 (M + 2); along with 1,2-bis(2-acetyl-
4-methylphenoxy)ethane (13b) (0.2 g, 12% yield) as a color-
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less solid; mp 127 °C. H NMR (200 MHz, CDCl3) δ: 2.31
(s, 6H), 2.57 (s, 6H), 4.44 (s, 4H), 6.9 (m, 2H), 7.2–7.2 (m,
2H), 7.54 (s, 2H). MS (70 eV) m/z: 326.
2-(2-Bromoethoxy)-propiophenone (6c) (1.55 g, 60%
yield) was obtained from 2-hydroxypropiophenone (1.5 g)
and 1,2-dibromoethane (11g) as a colorless solid; mp 36 °C.
1H NMR (200 MHz, CDCl3) δ: 1.17 (t, 3H, J = 7.1 Hz), 3.05
(t, 2H, J = 7.1 Hz), 3.69 (s, 3H), 3.69 (t, 2H, J = 5.9 Hz),
4.37 (t, 2H, J = 5.9 Hz), 6.8–7.7 (m, 4H). MS (70 eV) m/z:
256, 258 (M + 2); along with 1,2-bis(2-propionylphen-
oxy)ethane (13c) (0.3 g, 18% yield) as a colorless solid; mp
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97 °C. H NMR (200 MHz, CDCl3) δ: 1.08 (t, 6H, J =
7.3 Hz), 2.95 (quartet, 4H, J = 7.3 Hz), 4.45 (s, 4H), 7.0 (m,
4H), 7.4–7.6 (m, 2H), 7.7 (m, 2H). MS (70 eV) m/z: 326.
2-(2-Bromoethoxy)-4-methoxyacetophenone (6d) (1.65 g,
61% yield) was obtained from 2-hydroxy-4-methoxyaceto-
phenone (1.66 g) and 1,2-dibromoethane (11g) as a colorless
1-Benzyl-3-phenyl-4-methyl-5-(2-chloroethoxy)-(2,5)-di-
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hydro-2-pyrrolone (9i) was obtained as a colorless oil. H
NMR (200 MHz, CDCl3) δ: 2.11 (s, 3H), 3.3–3.6 (m, 4H),
© 2004 NRC Canada