Eco-friendly synthesis of β-nitro ketones from conjugated enones: An important improvement of the Miyakoshi procedure

Article abstract of DOI:10.1039/c1gc15616k

A variety of α,β-unsaturated ketones can be easily converted, at room temperature, into β-nitro ketones by nitration with solid supported nitrite (SSN) and in the presence of acetic acid and cyclopentyl methyl ether.

Full text of DOI:10.1039/c1gc15616k

Electronic Supplementary Material (ESI) for Green Chemistry
This journal is © The Royal Society of Chemistry 2011
SUPPORTING INFORMATION
Eco-Friendly Synthesis of β-Nitro Ketones from Conjugated Enones: An Important
Improvement of the Miyakoshi Procedure.
Serena Gabrielli,a Alessandro Palmieri,a Alvise Perosa,b Maurizio Selva,b and Roberto Ballini*a
a
Green Chemistry Group, School of Science and Technology, Chemistry Division, University of Camerino, Via S.
Agostino 1, 62032 Camerino, Italy.
Fax: +39 0737 402297; Tel: +39 0737 402270; E-mail: roberto.ballini@unicam.it
b
Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari Venezia, Dorsoduro 2137 – 30123
Venezia, Italy. Tel: +39 041 2348687; E-mail: selva@unive.it
Experimental Section
13
1H NMR were recorded at 400 MHz. C NMR were recorded at 100 MHz. GLC analyses were performed
on a capillary column of fused silica (0.32 mm×25 m), stationary phase SE54. Mass spectra were performed
on a GC/MS system by means of the EI technique (70 eV). Infrared spectra were recorded on a Perkin-Elmer
Spectrum One FT-IR spectrometer. Microanalyses were performed with a CHNS-O analyzer Model EA
1108 from Fisons Instruments.
General Procedure for the synthesis of compounds 1a-k.
Batch reaction was carried out by stirring a mixture of ketone 5 (1 mmol), SSN (3 mmol), acetic
acid (5 mmol) and CPME (3 mL). The reaction was allowed to stir for the appropriate time (see
Table 2) at room temperature. After the reaction was completed, the resin was filtered off washing
with EtOAc (5 mL), then the solvent was removed under vacuum, and the crude product 1 was
purified by flash chromatography column (hexanes: EtOAc = 85:15).
1a. Yield: 89%. White solid, m.p. 81-82°C. IR (cm-1, nujol) ν: 854, 1097, 1376,
1551, 1706. 1H-NMR (CDCl3, 400 MHz) δ: 2.86 (t, 2H, J = 6.8 Hz), 2.94 (t, 2H, J =
O
NO2
6.8 Hz), 3.02 (t, 2H, J = 6.0 Hz), 4.63 (t, 2H, J = 6.0 Hz), 7.15-7.33 (m, 5H). 13C-
NMR (CDCl3, 100 MHz) δ: 29.7, 38.7, 44.5, 69.1, 126.6, 128.5, 128.8, 140.6, 205.1. GC-MS (70eV): m/z:
207[M+], 160, 105, 91, 77, 65, 55(100). Anal. Calcd. for C11H13NO3 (207.23): C, 63.76; H, 6.32; N, 6.76.
Found: C, 63.84; H, 6.39; N, 6.72.
1b. Yield: 72%. Yellow waxy. IR (cm-1, nujol) ν: 870, 1091, 1380, 1560,
1705, 2917. H-NMR (CDCl3, 400 MHz) δ: 0.87 (t, 3H, J = 7.3 Hz), 1.20-
O
1
NO2
1.33 (m, 10H), 1.55-1.65 (m, 2H), 2.51 (t, 2H, J = 7.3 Hz), 3.05 (t, 2H, J =
6.0 Hz), 4.64 (t, 2H, J = 6.0 Hz). 13C-NMR (CDCl3, 100 MHz) δ: 14.3, 22.9, 23.8, 29.3, 29.5, 32.0, 38.5,
43.1, 69.2, 206.2. GC-MS (70eV): m/z: 169, 141, 97.7, 55(100), 29. Anal. Calcd. for C10H19NO3 (201.26):
C, 59.68; H, 9.52; N, 6.96. Found: C, 61.33; H, 9.92; N, 6.47.
1c. Yield: 82%. Yellow solid, m.p. 158-161°C. IR (cm-1, nujol) ν: 842, 968, 1374,
1557, 1603, 1684. 1H-NMR (CDCl3, 400 MHz) δ: 3.85 (t, 2H, J = 6.0 Hz), 4.95 (t,
O
NO2
2H, J = 6.0 Hz), 7.41-7.47 (m, 1H), 7.52 (t, 2H, J = 8.1 Hz), 7.76 (d, 2H, J = 8.1
Hz), 7.85 (d, 2H, J = 8.1 Hz), 8.16 (d, 2H, J = 8.1 Hz). 13C-NMR (CDCl3, 100
MHz) δ: 36.1, 70.7, 128.4, 128.5, 128.6, 129.7, 130.1, 130.4, 136.3, 140.9, 147.2,
196.7. GC-MS (70eV): m/z: 208, 181(100), 152, 127, 76, 55. Anal. Calcd. for C15H13NO3 (255.27): C,
70.58; H, 5.13; N, 5.49. Found: C, 70.65; H, 5.09; N, 5.45.

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1d. Yield: 86%. White waxy. IR (cm-1, nujol) ν: 870, 1107, 1366, 1550, 1685. H-NMR
(CDCl3, 400 MHz) δ: 3.67 (t, 2H, J = 6.0 Hz), 4.84 (t, 2H, J = 6.0 Hz), 7.51 (t, 2H, J =
7.3 Hz), 7.63 (t, 2H, J = 7.3 Hz), 8.00 (t, 2H, J = 7.3 Hz). 13C-NMR (CDCl3, 100 MHz) δ:
35.1, 69.5, 128.4, 129.1, 134.2, 135.9, 195.2. GC-MS (70eV): m/z: 179[M+], 105(100),
1
O
NO2
77, 55. Anal. Calcd. for C9H9NO3 (179.17): C, 60.33; H, 5.06; N, 7.82. Found: C, 60.37; H, 5.13; N, 7.90.
1e. Yield: 82%. Pink waxy. IR (cm-1, nujol) ν: 830, 1123, 1205, 1373, 1542, 1670.
O
1H-NMR (CDCl3, 400 MHz) δ: 3.60 (t, 2H, J = 6.0 Hz), 3.86 (s, 3H), 4.79 (t, 2H, J
NO2
= 6.0 Hz), 6.94 (d, 2H, J = 8.5 Hz), 7.94 (d, 2H, J = 8.5 Hz). 13C-NMR (CDCl3,
H3CO
100 MHz) δ: 34.6, 55.7, 69.6, 114.1, 128.9, 130.6, 164.3, 193.5. GC-MS (70eV):
m/z: 209[M+], 162, 135(100), 107, 92, 77, 63. Anal. Calcd. for C10H11NO4 (209.20): C, 57.41; H, 5.30; N,
6.70. Found: C, 57.50; H, 5.35; N, 6.65.
1f. Yield: 77%. Pink solid, m.p. 72-74°C. IR (cm-1, nujol) ν: 733, 836, 1112, 1376,
O
1550, 1685. 1H-NMR (CDCl3, 400 MHz) δ: 3.68 (t, 2H, J = 6.0 Hz), 4.85 (t, 2H, J =
NO2
6.0 Hz), 7.78 (d, 2H, J = 8.1 Hz), 8.09 (d, 2H, J = 8.1 Hz). 13C-NMR (CDCl3, 100
F3C
MHz) δ: 35.3, 69.1, 126.12, 126.16, 126.20, 126.23, 128.7, 135.2, 135.6, 138.4,
194.3. GC-MS (70eV): m/z: 200, 173(100), 145, 125, 95, 75, 55. Anal. Calcd. for C10H8F3NO3 (247.17): C,
48.59; H, 3.26; N, 5.67. Found: C, 48.67; H, 3.33; N, 5.61.
1g. Yield: 75%. Yellow waxy. IR (cm-1, nujol) ν: 1146, 1373, 1553, 1709, 2929. H-
1
O
NMR (CDCl3, 400 MHz) δ: 1.12-1.45 (m, 5H), 1.63-1.93 (m, 5H), 2.35-2.47 (m, 1H),
3.09 (t, 2H, J = 6.0 Hz), 4.63 (t, 2H, J = 6.0 Hz). 13C-NMR (CDCl3, 100 MHz) δ: 25.7,
25.9, 28.5, 36.6, 50.9, 69.3, 209.1. GC-MS (70eV): m/z: 185[M+], 111, 83(100), 55, 41.
NO2
Anal. Calcd. for C9H15NO3 (185.22): C, 58.36; H, 8.16; N, 7.56. Found: C, 58.45; H, 8.21; N, 7.61.
1h. Yield: 75%. Yellow solid, m.p. 72-75°C. IR (cm-1, nujol) ν: 870, 1165, 1380, 1564,
O
1664, 1731. 1H-NMR (CDCl3, 400 MHz) δ: 3.52 (t, 2H, J = 6.0 Hz), 4.79 (t, 2H, J = 6.0
NO2
Hz), 6.58 (dd, 1H, J = 1.7, 3.8 Hz), 7.27-7.29 (m, 1H), 7.62 (s, 1H). 13C-NMR (CDCl3,
O
100 MHz) δ: 34.7, 68.9, 112.9, 118.2, 147.2, 151.9, 184.1. GC-MS (70eV): m/z: 122, 95(100), 66, 55, 39.
Anal. Calcd. for C7H7NO4 (169.13): C, 49.71; H, 4.17; N, 8.28. Found: C, 49.77; H, 4.23; N, 8.22.
1i. Yield: 75%. White waxy. IR (cm-1, nujol) ν: 722, 1102, 1374, 1552, 1716,
2929. H-NMR (CDCl3, 400 MHz) δ: 1.40-1.49 (m, 2H), 1.60-1.68 (m, 2H),
O
Cl
1
NO2
1.73-1.82 (m, 2H), 2.54 (t, 2H, J = 6.8 Hz), 3.04 (t, 2H, J = 6.0 Hz), 3.53 (t, 2H,
J = 6.8 Hz), 4.64 (t, 2H, J = 6.0 Hz). 13C-NMR (CDCl3, 100 MHz) δ: 22.9, 26.5, 32.5, 38.5, 42.7, 45.0, 69.2,
205.8. GC-MS (70eV): m/z: 207[M+], 133, 117, 69(100), 55, 41. Anal. Calcd. for C8H14ClNO3 (207.65): C,
46.27; H, 6.80; N, 6.75. Found: C, 46.35; H, 6.83; N, 6.68.
1j. Yield: 84%. Yellow oil, IR (cm-1, nujol) ν: 863, 1057, 1376, 1559, 1718. H-NMR
1
O
(CDCl3, 400 MHz) δ: 1.09 (t, 3H, J = 7.3 Hz), 2.53 (q, 2H, J = 7.7, 14.5 Hz), 3.05 (t, 2H, J
NO2
= 6.0 Hz), 4.64 (t, 2H, J = 6.0 Hz). 13C-NMR (CDCl3, 100 MHz) δ: 7.7, 36.2, 38.0, 69.2,
206.6. GC-MS (70eV): m/z: 131[M+], 102, 57(100), 29. Anal. Calcd. for C5H9NO3 (131.13): C, 45.80; H,
6.92; N, 10.68. Found: C, 45.87; H, 6.98; N, 10.62.

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1k. Yield: 60%. Yellow oil. IR (cm-1, nujol) ν: 865, 1103, 1374, 1550, 1715. 1H-NMR
O
(CDCl3, 400 MHz) δ: 0.90 (t, 3H, J = 7.3 Hz), 1.24-1.36 (m, 2H), 1.50-1.60 (m, 5H),
2.40-2.49 (m, 2H), 2.66-2.73 (m, 1H), 3.31 (dd, 1H, J = 8.5, 18.0 Hz), 4.93-5.04 (m,
NO2
1H). 13C-NMR (CDCl3, 100 MHz) δ: 14.0, 19.6, 22.4, 25.7, 42.8, 46.1, 77.9, 206.4. GC-MS (70eV): m/z:
145, 131, 101, 85(100), 69, 57, 41, 29. Anal. Calcd. for C8H15NO3 (173.21): C, 55.47; H, 8.73; N, 8.09.
Found: C, 55.57; H, 8.78; N, 8.04.