derivatives described in the literature.18 1-Chloro-2-(4-iodophenyl)-
2-methylpropane (2b) was prepared by iodination of 1-chloro-2-
methyl-2-phenylpropane following the procedure by Barluenga and
col,19 using IPy2BF4 as iodinating agent.
The procedure followed in the reactions of compounds 2 with
the anions 3a,b is presented in Supporting Information and is as
previously described.1b
2-(4-Bromophenyl)-1-chloro-2-methylpropane (2a). Isolated
as colorless oil after distillation at reduced pressure. 1H NMR
(acetone-d6) δ 1.41 (s, 6H), 3.54 (s, 2H), 7.41 (d, 2H, J ) 8.9 Hz),
7.51 (d, 2H, J ) 8.9 Hz). 13C NMR (CDCl3) δ 26.3, 39.5, 55.7,
120.3, 127.7, 131.2, 144.8. m/z 248 (13.1), 246 (11.4), 199 (100.0),
197 (98.5), 171 (23.9), 169 (30.8), 118 (37.1), 117 (24.5), 116
(23.2), 115 (27.2), 91 (7.5), 77 (5.8), 51 (6.5). HRMS calcd for
C10H12BrCl 245.98109, 247.97814 (247.97904), 249.97609; found
245.98156, 247.979598, 249.97693.
129.3, 130.9, 132.2, 146.8, 213.0. m/z 273 (20.6), 231 (10.6), 230
(60.8), 217 (4.4), 215 (7.5), 187 (37.3), 146 (9.1), 145 (11.5), 131
(9.0), 105 (8.8), 104 (15.4), 103 (4.1), 85 (16.8), 57 (100). HRMS
calcd for C22H34O2 [M +1] 331.25588; found 330.2642.
2-[4-(2-Chloro-1,1-dimethyl-ethyl)-phenyl]-1-phenyl-etha-
none (1b). Isolated by column chromatography as a pale yellow
oil.1H NMR (acetone-d6) δ 1.39 (s, 6H), 3.75 (s, 2H), 4.35 (s, 2H),
7.2-8.2 (m, 9H). 13C NMR (CDCl3) δ 26.4, 26.5, 39.6, 44.9, 55.6,
56.3, 126.2, 126.3, 128.5, 128.6, 129.5, 130.2, 130.3, 132.6, 133.2,
133.7, 136.7, 144.6, 197.6. m/z 289 (2.1), 288 (1.3), 287 (6.6), 238
(4.0), 237 (3.3), 195 (4.0), 182 (3.1), 147 (1.7), 133 (7.4), 132 (10.8),
117 (12.5), 107 (12.1), 106 (100), 105 (100.0), 104 (40.4), 91 (6.0),
78 (9.7), 77 (46.1). HRMS calcd for C18H19ClO [M +1] 287.12027,
289.11732; found 287.12054, 289.11840.
1-Chloro-2-(4-iodophenyl)-2-methylpropane (2b). Isolated as
pale yellow oil after distillation at reduced pressure. 1H NMR (CCl4)
δ 1.4 (s, 6H), 3.6 (s, 2H), 7.17 (d, 2H, J ) 9.6 Hz), 7.71 (d, 2H,
J ) 9.6 Hz). 13C NMR (CDCl3) δ 26.3, 39.6, 55.7, 91.9, 128.0,
137.2, 145.5. m/z 296 (5.7), 294 (18.2), 246 (9.8), 245 (100.0),
217 (20.5), 127 (4.8), 118 (38.9), 117 (27.7), 116 (11.2), 115 (19.7),
91 (7.6), 77 (5.8), 51 (7.3). HRMS calcd for C10H12ClI 293.96723
(295.96428); found 293.96803 (295.96492).
2-[4-(2-Methyl-propenyl)-phenyl]-1-phenyl-ethanone (8b). Iso-
lated by column chromatography together with 8b′ (8b in higher
proportion according to GC relative peak areas). 1H NMR (acetone-
d6) δ 1.85 (m, 6H), 4.34 (s, 2H), 6.25 (s, 1H), 7.1-7.7 (m, 7H),
8.05 (d, 2H, J ) 10 Hz). m/z 251 (1.0), 250 (8.7), 145 (3.2), 129
(3.7), 128 (3.4), 115 (4.7), 106 (7.9), 105 (100.0), 77 (41.2). HRMS
calcd for C18H18O 250.13576; found 250.13548.
1-[4-(2-Chloro-1,1-dimethyl-ethyl)-phenyl]-3,3-dimethyl-2-bu-
tanone (1a). Isolated by column chromatography as colorless oil.
1H NMR (acetone-d6) δ 1.19 (s, 9H), 1.40 (s, 6H), 3.76 (s, 2H),
3.87 (s, 2H), 7.16 (d, 2H, J ) 8.3 Hz), 7.36 (d, 2H, J ) 8.3 Hz).
13C NMR (CDCl3) δ 26.5, 39.7, 42.8, 44.8, 56.5, 126.1, 129.7,
133.3, 144.5, 213.1. m/z 266 (1.5), 230 (5.4), 181 (3.0), 145 (10.6),
133 (7.5), 117 (5.4), 105 (2.5), 85 (20.0), 57 (100.0). HRMS calcd
for C16H23ClO [M + 1] 267.15157, 269.14862; found 267.15096,
269.14988.
2-[4-(2-Methyl-allyl)-phenyl]-1-phenyl-ethanone (8b′). Isolated
by column chromatography together with 8b (8b in higher
proportion according to GC relative peak areas). 1H NMR (acetone-
d6) δ 1.64 (s, 3H), 3.30 (s, 2H), 4.3 (s, 2H), 4.75 (m, 2H), 7.1-7.7
(m, 7H), 8.05 (d, 2H, J ) 10 Hz). m/z 251 (4.5), 250 (25.3), 146
(3.8), 145 (31.9), 130 (4.7), 129 (10.3), 128 (11.2), 115 (11.1), 106
(7.5), 105 (100.0), 77 (40.1). HRMS calcd for C18H18O 250.13576;
found 250.13548.
1-(4-Isobutyl-phenyl)-3,3-dimethyl-butan-2-one (7a). Isolated
by column chromatography as colorless oil. 1H NMR (acetone-d6)
δ 0.89 (d, 6H, J ) 6.6 Hz), 1.18 (s, 9H), 1.78-1.91 (m, 1H), 2.45
(d, 2H, J ) 7.3 Hz), 3.84 (s, 2H), 7.08 (s, 4H). 13C NMR (CDCl3)
δ 22.4, 26.4, 30.1, 42.9, 44.6, 45.0, 129.1, 129.2, 132.1, 140.0,
213.1. m/z 232 (3.0), 147 (6.2), 131 (1.6), 115 (2.1), 105 (11.4),
104 (5.2), 85 (12.1), 77 (3.7), 57 (100.0). HRMS calcd for C16H24O
232.18272; found 232.18283.
3,3-Dimethyl-4-[4-(2-oxo-2-phenyl-ethyl)-phenyl]-1-phenyl-1-
butanone (9b). Isolated by column chromatography as yellow oil.
1H NMR (acetone-d6) δ 1.05 (s, 6H); 2.8 (s, 2H), 2.9 (s, 2H), 4.3
(s, 2H), 7.15 (d, 2H, J ) 8.0 Hz), 7.23 (d, 2H, J ) 8.0 Hz), 7.4-
7.6 (m, 6H), 7.95 (d, 2H, J ) 6.9 Hz), 8.09 (d, 2H, J ) 6.9 Hz).
13C NMR (acetone-d6) δ 27.4, 35.0, 45.0, 47.5, 47.6, 128.4, 128.9,
129.0, 129.1, 129.6, 131.1, 133.1, 133.4, 137.4, 137.7, 197.6, 200.1.
m/z 250 (33.0), 145 (8.3), 105 (100.0), 77 (44.6). HRMS calcd for
C26H26O2 [M + 1] 371.20111; found 371.20218.
3,3-Dimethyl-1-[4-(2-methyl-prop-1-enyl)-phenyl]-butan-2-
1
one (8a). Isolated by column chromatography as colorless oil. H
NMR (acetone-d6) δ 1.15 (s, 9H), 1.84 (d, 3H, J ) 1.2 Hz), 1.87
(d, 3H, J ) 1.4 Hz), 3.85 (s, 2H), 6.25 (m, 1H), 7.1 (m, 4H). m/z
231 (8.8), 230 (37.4), 146 (16.8), 145 (100.0), 129 (16.5), 128
(16.0), 115 (13.8), 105 (11.7), 85 (13.3), 77 (13.1), 57 (94.1), 41
(36.1). HRMS calcd for C16H22O 230.167066; found 230.167508.
6-[4-(3,3-Dimethyl-2-oxo-butyl)-phenyl]-2,2,5,5-tetramethyl-
hexan-3-one (9a). Isolated by column chromatography as a pale
1-(4-tert-Butyl-phenyl)-3,3-dimethyl-butan-2-one (11a).20 Iso-
lated by column chromatography as a colorless oil. 1H NMR
(acetone-d6) δ 1.17 (s, 18H), 3.80 (s, 2H), 7.1 (m, 4H). m/z 233
(1.1), 232 (5.2), 147 (10.7), 133 (8.4), 85 (17.8), 57 (100.0). 11a
was compared with an authentic sample synthesized by reaction
of 4-bromo-tert-butylbenzene with 3a in DMSO, following the
general procedure described in Supporting Information.
1
yellow solid. H NMR (CDCl3) δ 0.99 (s, 6H), 1.09 (s, 9H), 1.19
(s, 9H), 2.31 (s, 2H), 2.73 (s, 2H), 3.76 (s, 2H), 7.05 (s, 4H). 13C
NMR (CDCl3) δ 26.4, 26.5, 27.5, 34.0, 42.9, 44.6, 44.7 45.4, 46.8,
128.9, 130.6, 132.5, 137.5, 231.1. m/z 330 (3.4), 273 (34.9), 245
(8.6), 217 (36.6), 203 (10.6), 187 (20.6), 155 (10.2), 132 (6.7), 117
(12.9), 105 (4.2), 104 (3.1), 85 (11.3), 57 (100). HRMS calcd for
C22H34O2 [M + 1] 331.25588; found 330.2637.
Acknowledgment. This work was supported by the Agencia
Co´rdoba Ciencia, CONICET and SECYT, Universidad Nacional
de Co´rdoba, Argentina. M.H.G. acknowledges receipt of a
fellowship from CONICET and from FOMEC. The authors
thank Prof. J. Barluenga Mur from the University of Oviedo,
Spain, for the assistance provided to the synthesis of 2b.
6-[4-(3,3-Dimethyl-2-oxo-butyl)-phenyl]-2,2,6-trimethyl-hep-
tan-3-one (10a). Isolated by column chromatography as a pale
1
yellow solid. H NMR (CDCl3) δ 1.02 (s, 9H), 1.20 (s, 9H), 1.29
(s, 6H), 1.87 (t, 2H, J ) 7.8 Hz), 2.21 (t, 2H, J ) 7.8 Hz), 3.77 (s,
2H), 7.11 (d, 2H, J ) 8.4 Hz), 7.25 (d, 2H, J ) 8.0 Hz). 13C NMR
(CDCl3) δ 26.3, 26.4, 27.6, 29.0, 32.2, 37.1, 38.0, 42.8, 44.6, 125.8,
Supporting Information Available: General methods; 1H NMR
and 13C NMR spectra of compounds 1, 2, and 7-10; computational
procedure and summary of B3LYP calculations for the radical
anions discussed. This material is available free of charge via the
(18) Ranu, B. C.; Sarkar, D. C.; Chakraborty, R. Synth. Commun. 1992,
22, 1095.
(19) Barluenga, J.; Gonza´lez, J. M.; Garc´ıa-Mart´ın, M. A.; Campos,
P. J.; Asensio, G. J. Org. Chem. 1993, 58, 2058.
(20) Bied, C.; Collin, J.; Kagan, H. B. Tetrahedron 1992, 48, 3877.
JO062457I
3092 J. Org. Chem., Vol. 72, No. 8, 2007