Bou-Moreno et al.
11
2-Chloro-2-nitrosopropylbenzene (18)33
CDCl3) ␦: 14.1 (CH3), 23.7 (CH3), 35.5 (CH2), 47.4 (CH3),
60.8 (CH2), 119.5 (C), 128.3 (CH), 128.6 (2CH), 129.9 (2CH),
136.5 (C), 170.7 (CO). MS m/z: 239 ([M – NO]ϩ), 240 ([M –
NO]ϩ), 241 ([M – NO]ϩ). HR-MS m/z ([M – NO]ϩ) calcd for
C13H1635ClO2: 239.0839; found: 239.0845.
Prepared from 2-nitropropylbenzene (165 mg, 1.00 mmol),
purification (petroleum spirit 100%) produced the correspond-
ing chloronitroso product (147 mg, 80%) as a deep blue oil. IR
(neat, cm–1): 3033, 2928, 1713, 1583, 1563, 1496, 1455, 1447,
1
1373, 1087, 736, 700. H NMR (400 MHz, CDCl3) ␦: 1.77
5-Chloro-5-nitrosohexan-2-ol (22)
(3H, m, CH3), 3.64–3.74 (2H, m, CH2), 7.15–7.22 (2H, m,
CH), 7.28–7.35 (3H, m, CH). 13C NMR (100 MHz, CDCl3) ␦:
23.7 (CH3), 44.4 (CH2), 115.5 (C), 127.6 (CH), 128.3 (CH),
128.7 (CH), 130.9 (CH), 133.6 (C). MS m/z: 153 ([M –
NO]ϩ), 154 ([M – NO]ϩ), 155 ([M – NO]ϩ). HR-MS m/z
([M – NO]ϩ) calcd for C9H1035Cl: 153.0471; found: 153.0469.
Prepared from 5-chloro-5-nitrohexan-2-one (290 mg,
2.00 mmol), purification (petroleum spirit/Et2O 90:10) pro-
duced the corresponding chloronitroso product (140 mg, 85%)
as a deep blue oil. IR (neat, cm–1): 3308, 2969, 2932, 1582,
1
1445, 1375, 1134, 1032, 931. H NMR (600 MHz, C6D6) ␦:
0.82–0.88 (3H, m, CH3), 0.97–1.10 (1H, m, CH2), 1.41 (3H, s,
CH3), 1.91–2.01 (1H, m, CH2), 2.57–2.67 (1H, m, CH2),
3.30–3.40 (1H, m, CH2). 13C NMR (150 MHz, C6D6) ␦: 23.5
(CH3), 24.1 (CH3), 33.0 (CH2), 35.2 (CH2), 67.0 (CH), 117.4
(C). MS m/z: 166 ([M ϩ H]ϩ). HR-MS m/z ([M ϩ H]ϩ) calcd
for C6H13NO235Cl: 166.0635; found: 166.0625.
Methyl 4-chloro-4-nitrosopentanoate (19)
Prepared from 4-methyl-4-nitropentanoate (161 mg,
1.00 mmol), purification (petroleum spirit/Et2O 98:2) pro-
duced the corresponding chloronitroso product (127 mg, 72%)
as a deep blue oil. IR (neat, cm–1): 2955, 1737, 1585, 1563,
1438, 1197, 1174. 1H NMR (400 MHz, CDCl3) ␦: 1.80 (3H, s,
CH3), 2.14–2.24 (1H, m, CH2), 2.36–2.46 (1H, m, CH2),
2.57–2.67 (1H, m, CH2), 2.88–2.98 (1H, m, CH2), 3.67 (3H,
s, CH3). 13C NMR (100 MHz, CDCl3) ␦: 24.2 (CH3), 28.5
(CH2), 33.4 (CH2), 51.9 (CH3), 115.5 (C), 172.3 (CO). MS
m/z: 149 ([M – NO]ϩ) 150 ([M – NO]ϩ), 151 ([M – NO]ϩ).
HR-MS m/z ([M – NO]ϩ) calcd for C6H1035ClO2: 149.0364;
found: 149.0368.
Acknowledgements
The authors would like to thank Dr. A.E. Aliev for his
collaboration on the NMR study and Dr. S. Coles for his
collaboration on the X-ray diffraction. The authors would also
like to thank Dr.Dr. R. Hay-Motherwell for her generous
permission to finance this study.
References
Methyl 4-chloro-4-nitrosohept-6-enoate (20)
Prepared from methyl 4-nitrohept-6-enoate (187 mg,
1.00 mmol), purification (petroleum spirit/Et2O 98:2) pro-
duced the corresponding chloronitroso product (150 mg, 73%)
as a deep blue oil. IR (neat, cm–1): 2954, 1737, 1582, 1563,
(1) (a) Pulacchini, S.; Sibbons, K. F.; Shastri, K.; Motevalli, M.;
Watkinson, M.; Wan, H.; Whiting, A.; Lightfoot, A. P. Dalton
K. R.; Lightfoot, A. P.; Wan, H.; Whiting, A. J. Chem. Soc.,
Iwasa, S.; Fakhruddin, A.; Tsukamoto, Y.; Kameyama, M.;
Nishiyama, H. Tetrahedron Lett. 2002, 43 (35), 6159. doi:
Tsushima, S.; Nishiyama, H. Tetrahedron Lett. 2001, 42 (34),
Lightfoot, A. P.; Wan, H.; Whiting, A. Chem. Commun.
N. E.; Ware, R. W., Jr.; Atkinson, R. N.; King, S. B. Synth.
(g) Martin, S. F.; Hartmann, M.; Josey, J. A. Tetrahedron Lett.
Kirby, G. W.; Sweeny, J. G. J. Chem. Soc. Chem. Commun.
(2) (a) Streith, J.; Defoin, A. Synlett 1996, 1996 (03), 189. doi:
and Nitroso Groups; John Wiley: New York, 1969.
(3) For a review of spin traps see Janzen, E. G. Acc. Chem. Res.
(4) (a) Yamamoto, Y.; Kawasaki, M. Bull. Chem. Soc. Jpn. 2007,
N. Synthesis 2005, 20, 3565; (c) Yamamoto, Y.; Yamamoto, H.
J. Am. Chem. Soc. 2004, 126 (13), 4128. doi:10.1021/
ja049849w; (d) Gouverneur, V.; Ghosez, L. Tetrahedron 1996,
(5) (a) Guo, H.-M.; Cheng, L.; Cun, L.-F.; Gong, L.-Z.; Mi, A.-Q.;
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1
1437, 1199, 1174. H NMR (400 MHz, CDCl3) ␦: 1.96–2.06
(1H, m, CH2), 2.30–2.40 (1H, m, CH2), 2.63–2.73 (1H, m,
CH2), 3.26–3.04 (3H, m, CH2), 3.68 (3H, s, CH3), 5.16–5.25
(2H, m, CHallyl), 5.54–5.66 (1H, m, CHallyl). 13C NMR
(100 MHz, CDCl3) ␦: 28.0 (CH2), 32.0 (CH2), 41.7 (CH2),
51.9 (CH3), 119.1 (C), 121.2 (CH2), 129.4 (CH), 172.3 (CO).
MS m/z: 206 ([M ϩ H]ϩ), 207 ([M ϩ H]ϩ), 208 ([M ϩ H]ϩ).
HR-MS m/z ([M ϩ H]ϩ) calcd for C8H13NO335Cl: 206.0584;
found: 206.0589.
5-Chloro-5-nitrosohexan-2-one (21)
Prepared from 5-chloro-5-nitrohexan-2-one (290 mg,
2.00 mmol), purification (petroleum spirit/Et2O 98:2) pro-
duced the corresponding chloronitroso product (75 mg, 23%)
as a deep blue oil. IR (neat, cm–1): 2933, 1718, 1584, 1564,
1424, 1365, 1167. 1H NMR (400 MHz, CDCl3) ␦: 1.84 (3H, s,
CH3), 2.15 (3H, s, CH3), 2.24–2.34 (1H, m, CH2), 2.46–2.63
(2H, m, CH2), 2.89–2.99 (1H, m, CH2). 13C NMR (100 MHz,
CDCl3) ␦: 24.6 (CH3), 30.0 (CH2), 32.0 (CH2), 38.4 (CH3),
116.2 (C), 206.2 (CO).
Ethyl 4-chloro-4-nitroso-3-phenylpentanoate (23)
Prepared from ethyl 4-nitro-3-phenylpentanoate (251 mg,
1.00 mmol), purification (petroleum spirit/Et2O 98:2) pro-
duced the corresponding chloronitroso product (185 mg, 69%)
as a deep blue oil. IR (neat, cm–1): 2982, 1733, 1582, 1455,
1
1374, 1160. H NMR (600 MHz, CDCl3) ␦: 1.04 (3H, t, J ϭ
7.2 Hz, CH3), 1.47 (3H, s, CH3), 2.18 (1H, dd, J ϭ 16.1, 4 Hz,
CH2), 2.79 (1H, dd, J ϭ 16.1, 10.8 Hz, CH2), 3.92 (2H, m,
CH2), 5.00 (1H, dd, J ϭ 10.8, 4.0 Hz, CH), 7.31–7.38 (3H, m,
CHAr), 7.43–7.47 (2H, m, CHAr). 13C NMR (150 MHz,
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