The Journal of Organic Chemistry
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0.85 (s, 6 H), 1.89 (s, 4 H), [ABC system at δ = 4.94 (J = −12.7, 6.3
Hz), 5.04 (J = 6.3, 9.3 Hz), 5.51 (J = −12.7, 9.3 Hz)], 7.49−7.51 (m, 2
H), 7.59−7.61 (m, 2 H). 13C NMR (100 MHz, DMSO-d6): δ (ppm) =
28.6, 31.3, 38.8, 50.2, 78.2, 107.1, 107.7, 119.2, 128.5, 131.4, 150.3,
187.2.
chromatography (silica gel 70−230 mesh; gradient eluent: n-
pentane/ethyl acetate = 11/1 to 4/1) and then recrystallized from
ethanol: 100 mg (0.340 mmol, 50%), yellowish solid, mp 127−130 °C.
1H NMR (300 MHz, CDCl3): δ (ppm) = 2.03 (s, 3 H), 2.32 (s, 3 H),
[ABCD system at δ = 4.38 (J = 4.0, 8.9, 10.1 Hz), 4.39 (J = 10.1 Hz),
4.66 (J = −13.0, 4.0 Hz), 4.69 (J = −13.0, 8.9 Hz)], 7.38−7.43 (m, 2
H), 8.18−8.21 (m, 2 H). 13C NMR (75.5 MHz, CDCl3): δ (ppm) =
30.1, 30.7, 42.4, 70.2, 77.5, 124.6, 129.3, 143.7, 148.0, 200.0, 200.9.
Anal. Calcd for C13H14N2O6: C, 53.06; H, 4.80; N, 9.52. Found: C,
53.07; H, 4.89; N, 9.52.
Potassium 4,4-Dimethyl-1-(2-nitro-1-(4-nitrophenyl)ethyl)-2,6-di-
oxocyclohexan-1-ide (4fb-K). From 1f and 2b-K by following general
1
procedure A. H NMR (400 MHz, DMSO-d6): δ (ppm) = 0.84 (s, 6
H), 1.87 (s, 4 H), [ABC system at δ = 4.92 (J = −12.8, 5.9 Hz), 5.10 (J
= 5.9, 9.5 Hz), 5.59 (J = −12.8, 9.5 Hz)], 7.57−7.59 (m, 2 H), 8.01−
8.04 (m, 2 H). 13C NMR (100 MHz, DMSO-d6): δ (ppm) = 28.7,
31.2, 38.8, 50.5, 78.2, 106.7, 122.6, 128.5, 145.0, 153.0, 187.4.
3-(1-(4-Methoxyphenyl)-2-nitroethyl)pentane-2,4-dione (5ac).
Obtained from 1a (129 mg, 0.720 mmol) and 2c-H following general
procedure B: 158 mg (0.566 mmol, 79%), yellow solid, mp 115−117
°C. 1H NMR (300 MHz, CDCl3): δ (ppm) = 1.94 (s, 3 H), 2.28 (s, 3
H), 3.77 (s, 3 H), [ABCD system at δ = 4.19 (J = 4.5, 8.3, 11.0 Hz),
4.33 (J = 11.0 Hz), 4.58 (J = −12.4, 4.5 Hz), 4.59 (J = −12.4, 8.3
Hz)], 6.81−6.86 (m, 2 H), 7.07−7.12 (m, 2 H). 13C NMR (75.5 MHz,
CDCl3): δ (ppm) = 29.6, 30.5, 42.2, 55.4, 71.0, 78.6, 114.8, 127.7,
129.2, 159.6, 201.3, 202.0. Anal. Calcd for C14H17NO5: C, 60.21; H,
6.14; N, 5.02. Found: C, 60.07; H, 6.17; N, 4.99.
Ethyl 2-Acetyl-4-nitro-3-phenylbutanoate (5cd). Obtained from
1c (160 mg, 1.07 mmol) and 2d-H following general procedure B: 165
1
mg (0.591 mmol, 55%, dr ≈ 1:8 from H NMR integrals of the CH3
signals of CH3CO and OCH2CH3), colorless solid, mp 73−75 °C. 1H
NMR (300 MHz, CDCl3, major diastereomer): δ (ppm) = 1.00 (t, J =
7.1 Hz, 3 H), 2.30 (s, 3 H), 3.96 (q, J = 7.1 Hz, 2 H), [ABCD system
at δ = 4.09 (J = 10.0 Hz), 4.17 (J = 4.6, 8.3, 10.0 Hz), 4.72 (J = −13.1,
8.3 Hz), 4.72 (J = −13.1, 4.6 Hz)], 7.18−7.21 (m, 2 H), 7.26−7.34
(m, 3 H); additional signals for the minor diastereomer: δ (ppm) =
1.27 (t, J = 7.1 Hz, 0.4 H), 2.05 (s, 0.4 H). 13C NMR (75.5 MHz,
CDCl3, major diastereomer): δ (ppm) = 13.8, 30.2, 42.4, 62.1, 78.0,
128.1, 128.4, 129.1, 136.5, 167.0, 201.3. HRMS (ESI): calcd for
C14H16NO5 [M − H]−, 278.1034; found, 278.1038. Anal. Calcd for
−
3-(2-Nitro-1-p-tolylethyl)pentane-2,4-dione (5bc). Obtained from
1b (124 mg, 0.760 mmol) and 2c-H following general procedure B:
C14H17NO5: C, 60.21; H, 6.14; N, 5.02. Found: C, 60.14; H, 6.28; N,
4.98.
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142 mg (0.539 mmol, 71%), colorless solid, mp 104 °C. H NMR
(400 MHz, CDCl3): δ (ppm) = 1.93 (s, 3 H), 2.28 (s, 3 H), 2.30 (s, 3
H), [ABCD system at δ = 4.20 (J = 4.4, 8.5, 10.9 Hz), 4.35 (J = 10.9
Hz), 4.59 (J = −12.3, 4.4 Hz), 4.60 (J = −12.3, 8.5 Hz)], 7.04−7.07
(m, 2 H), 7.11−7.13 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ
(ppm) = 21.2, 29.6, 30.6, 42.6, 70.9, 78.5, 127.9, 130.1, 132.9, 138.5,
201.3, 202.0. Anal. Calcd for C14H17NO4: C, 63.87; H, 6.51; N, 5.32.
Found: C, 63.83; H, 6.53; N, 5.31.
Potassium 1,1-Dicyano-3-nitro-2-phenylpropan-1-ide (4ce-K).
From 1c and 2e-K by following general procedure A. H NMR (400
MHz, DMSO-d6): δ (ppm) = [ABC system at δ = 3.70 (J = 8.2, 8.4
Hz), 4.67 (J = −12.3, 8.4 Hz), 4.70 (J = −12.3, 8.2 Hz)], 7.18−7.31
(m, 5 H). 13C NMR (100 MHz, DMSO-d6): δ (ppm) = 40.0, 43.0,
79.8, 126.6, 127.0, 128.3, 129.9, 142.5.
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Ethyl 2-Cyano-4-nitro-3-phenylbutanoate (5cf). Obtained from
3-(2-Nitro-1-phenylethyl)pentane-2,4-dione (5cc). Obtained
from 1c (179 mg, 1.20 mmol) and 2c-H following general procedure
B: 212 mg (0.851 mmol, 71%), pale yellow solid, mp 111−112 °C. 1H
NMR (300 MHz, CDCl3): δ (ppm) = 1.93 (s, 3 H), 2.28 (s, 3 H),
[ABCD system at δ = 4.21 (J = 4.3, 8.5, 10.8 Hz), 4.34 (J = 10.8 Hz),
4.59 (J = −12.4, 4.3 Hz), 4.61 (J = −12.4, 8.5 Hz)], 7.16−7.20 (m, 2
H), 7.28−7.36 (m, 3 H). 13C NMR (75.5 MHz, CDCl3): δ (ppm) =
29.7, 30.6, 42.9, 70.8, 78.3, 128.1, 128.7, 129.5, 136.1, 201.1, 201.9.
Anal. Calcd for C13H15NO4: C, 62.64; H, 6.07; N, 5.62. Found: C,
62.51; H, 6.04; N, 5.60.
3-(1-(4-Bromophenyl)-2-nitroethyl)pentane-2,4-dione (5dc). Ob-
tained from 1d (141 mg, 0.618 mmol) and 2c-H following general
procedure B: 127 mg (0.387 mmol, 63%), colorless solid, mp 135−137
°C. 1H NMR (300 MHz, CDCl3): δ (ppm) = 1.97 (s, 3 H), 2.29 (s, 3
H), [ABCD system at δ = 4.21 (J = 3.8, 8.9, 10.8 Hz), 4.32 (J = 10.8
Hz), 4.60 (J = −12.6, 3.8 Hz), 4.61 (J = −12.6, 8.9 Hz)], 7.05−7.09
(m, 2 H), 7.44−7.48 (m, 2 H). 13C NMR (75.5 MHz, CDCl3): δ
(ppm) = 29.8, 30.6, 42.3, 70.6, 78.0, 122.8, 129.8, 132.6, 135.2, 200.7,
201.5. Anal. Calcd for C13H14BrNO4: C, 47.58; H, 4.30; N, 4.27.
Found: C, 47.56; H, 4.40; N, 4.22.
trans-β-nitrostyrene (1c) (298 mg, 2.00 mmol) and 2f-H following
general procedure B: 349 mg (1.33 mmol, 67%, dr ≈ 1.4:1 from H
1
NMR integrals of the CH3 signals), colorless oil. 1H NMR (400 MHz,
CDCl3, major diastereomer): δ (ppm) = 1.13 (t, J = 7.2 Hz, 1.6 H),
[ABCD system at δ = 3.93 (J = 5.7 Hz), 4.22 (J = 5.7, 6.2, 8.7 Hz),
4.92 (J = −13.6, 8.7 Hz), 5.01 (J = −13.6, 6.2 Hz)], 7.21−7.39 (m, 5
H); additional signals for the minor diastereomer: δ (ppm) = 1.22 (t, J
= 7.2 Hz, 1.2 H), 4.09−4.15 (m, 1.6 H), 4.75−4.85 (m, 0.9 H). 13C
NMR (100 MHz, CDCl3, major diastereomer): δ (ppm) = 13.8, 41.7,
42.8, 63.4, 76.1, 76.4, 114.4, 127.6, 128.0, 129.4, 129.5, 163.9.
Diethyl 2-(2-Nitro-1-phenylethyl)malonate (5cg). trans-β-Nitro-
styrene (1c) (97 mg, 0.65 mmol) and 2g-K (129 mg, 0.651 mmol)
were dissolved in dry 1,4-dioxane (15 mL) and stirred for 10 min
under nitrogen atmosphere. Subsequent addition of 2 M aqueous
acetic acid (1 mL) furnished a precipitate, which was filtered. The
crude product was purified by column chromatography (silica gel 70−
230 mesh; gradient eluent: n-pentane/ethyl acetate =10/1 to 3/1) and
then recrystallized from ethanol: 82 mg (0.27 mmol, 42%), yellow
solid, mp 63−64 °C. 1H NMR (300 MHz, CDCl3): δ (ppm) = 1.04 (t,
J = 7.1 Hz, 3 H), 1.26 (t, J = 7.1 Hz, 3 H), 4.00 (q, J = 7.1 Hz, 2 H),
4.21−4.27 (m, 2 H), [ABCD system at δ = 3.79 (J = 9.4 Hz), 4.20 (J =
4.6, 9.4, 9.4 Hz), 4.83 (J = −13.1, 9.4 Hz), 4.89 (J = −13.1, 4.6 Hz)],
7.22−7.32 (m, 5 H). 13C NMR (75.5 MHz, CDCl3): δ (ppm) = 13.9,
14.1, 43.1, 55.1, 62.0, 62.3, 77.8, 128.1, 128.5, 129.0, 136.3, 166.9,
167.6.
4-(3-Acetyl-1-nitro-4-oxopent-2-yl)benzonitrile (5ec). Obtained
from 1e (127 mg, 0.729 mmol) and 2c-H following general procedure
B. The crude product was purified by column chromatography (silica
gel 70−230 mesh; gradient eluent: n-pentane/ethyl acetate = 12/1 to
3/1) and then recrystallized from ethanol: 76 mg (0.28 mmol, 38%),
1
colorless solid, mp 127−128 °C. H NMR (300 MHz, CDCl3): δ
(1,3-Dinitroprop-2-yl)benzene (5ch). trans-β-Nitrostyrene (1c)
(171 mg, 1.15 mmol) was dissolved in nitromethane (10 mL) under
nitrogen atmosphere; then, triethylamine (1 mol %) was added. The
mixture was stirred at ambient temperature for 24 h. The solvent was
removed in vacuo, and then, the crude product was purified by column
chromatography (silica gel 70−230 mesh; gradient eluent: n-pentane/
ethyl acetate =10/1 to 3/1): 121 mg (0.576 mmol, 50%), colorless oil.
1H NMR (400 MHz, CDCl3): δ (ppm) = [AA′BB′C system at δ = 4.31
(J = 7.0, 7.4 Hz), 4.75 (J = −13.4, 7.4 Hz), 4.78 (J = −13.4, 7.0 Hz)],
7.21−7.24 (m, 2 H), 7.36−7.41 (m, 3 H). 13C NMR (100 MHz,
CDCl3): δ (ppm) = 41.8, 76.8, 127.5, 129.2, 129.7, 134.3.
1-(6-(2-Nitro-1-phenylethyl)cyclohex-1-enyl)pyrrolidine (rac-
7ca). trans-β-Nitrostyrene (1c) (298 mg, 2.00 mmol) and 1-
(ppm) = 2.00 (s, 3 H), 2.31 (s, 3 H), [ABCD system at δ = 4.31 (J =
4.1, 8.7, 10.6 Hz), 4.36 (J = 10.6 Hz), 4.64 (J = −13.0, 4.1 Hz), 4.66 (J
= −13.0, 8.7 Hz)], 7.31−7.35 (m, 2 H), 7.62−7.66 (m, 2 H). 13C
NMR (75.5 MHz, DMSO-d6): δ (ppm) = 30.1, 30.7, 42.7, 70.1, 77.5,
112.8, 118.1, 129.0, 133.1, 141.7, 200.1, 201.0. Anal. Calcd for
C14H14N2O4: C, 61.31; H, 5.14; N, 10.21. Found: C, 61.14; H, 5.30;
N, 10.19. IR (ATR) ν (cm−1) = 726, 833, 860, 956, 1075, 1119, 1144,
1176, 1211, 1242, 1268, 1361, 1419, 1439, 1508, 1555, 1609, 1701,
1732.
3-(2-Nitro-1-(4-nitrophenyl)ethyl)pentane-2,4-dione (5fc). Ob-
tained from 1f (132 mg, 0.680 mmol) and 2c-H following general
procedure B. The crude product was purified by column
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dx.doi.org/10.1021/jo201678u|J. Org. Chem. 2011, 76, 9370−9378