148 JOURNAL OF CHEMICAL RESEARCH 2013
1,3-Dinitro-2-[4-dimethylaminophenyl]propane (2j): Reddish-
brown crystal, m.p.111–112 °C (lit.22 111–112 °C); Rf = 0.30 (PE/
AcOEt = 4:1); 1H NMR (400 MHz, CDCl3) δ 2.96 (s, 6H), 4.18–4.26
(m, 1H), 4.69–4.78 (m, 4H), 6.69 (d, J = 8.8 Hz, 2H), 7.08 (d, J = 8.8 Hz,
2H).
Conclusions
In this study, a nickel complex/Zn combination was found
to be highly active for the synthesis of 1, 3-dinitroalkanes in
excellent yields. This protocol is undoubtedly general and
could provide many opportunities for further study on related
chemistry. Studies on the scope and reaction mechanism of
this novel finding are underway.
1,3-Dinitro-2-phenyl-propane (2k):23 Brownish oil; Rf = 0.46 (PE/
1
AcOEt = 4:1); H NMR (400 MHz, CDCl3) δ 4.29–4.36 (m, 1H),
4.73–4.83 (m, 4H), 7.23–7.25(m, 2H), 7.34–7.42(m, 3H).
1,3-Dinitro-2-[4-chlorophenyl]propane (2l): Yellow crystal, m.p.
1
79–81 °C (lit.11 79–81 °C); Rf = 0.35 (PE/AcOEt = 4:1); H NMR
Experimental
(400 MHz, CDCl3) δ 4.28–4.35 (m, 1H), 4.72–4.82 (m, 4H), 7.19 (d,
J = 8.28 Hz, 2H), 7.38 (d, J = 8.53 Hz, 2H).
All reactions were carried out in an oven-dried flask in air atmosphere.
Organic solvents were dried and distilled as described elsewhere18. 1H
NMR (400 MHz) and 13C NMR (100 MHz) were recorded on Bruker
spectrometers with CDCl3 as the solvent and tetramethylsilane (TMS)
as the internal standard. Chemical shifts for 1H NMR are expressed in
1,3-Dinitro-2-[4-bromophenyl]propane (2m): Yellowish crystal,
m.p. 80–82 °C (lit.20 81–82 °C); Rf = 0.46 (PE/AcOEt = 4:1); 1H NMR
(400 MHz, CDCl3) δ 4.26–4.33 (m, 1H), 4.71–4.81 (m, 4H), 7.13 (d,
J = 8.3 Hz, 2H), 7.53 (d, J = 8.3 Hz, 2H).
ppm relative to tetramethylsilane (δ 0.0 ppm). Chemical shifts for 13
C
1,3-Dinitro-2-[3-trifluoromethylphenyl]propane (2n):7 Yellowish
crystal, m.p. 65–67 °C; Rf = 0.44 (PE/ AcOEt = 4:1); 1H NMR
(400 MHz, CDCl3) δ 4.40–4.47 (m, 1H), 4.78–4.88 (m, 4H), 7.47 (d,
J = 7.53 Hz, 1H), 7.53–7.58 (m, 2H), 7.66 (d, J = 7.8, 1H).
1,3-Dinitro-2-[3 nitrophenyl]propane (2o):11 Dark yellow oil; Rf =
NMR are expressed in ppm relative to CDCl3 (δ 77.0 ppm). Data are
presented as follows: chemical shift (ppm), multiplicity (s = singlet,
d = doublet, t = triplet, m = multiplet, br = broad), coupling constant
J (Hz) and integration. Gas chromatography/mass spectra (GC/MS)
were recorded on an Agilent Technologies 6890 N instrument with an
Agilent 5973 N electron ionisation (EI) system. Analytical TLC was
performed on TLC silica gel plates (0.25 mm) precoated with a fluo-
rescent indicator. Standard flash chromatography procedures were
followed using 32–63 µm silica gel. Visualisation was effected with
UV light, KMnO4, phosphomolybdic acid (PMA) or ethanol sulfuric
acid.
1
0.33 (PE/AcOEt = 10:1); H NMR (400 MHz, CDCl3) δ 4.47–4.54
(m, 1H), 4.82–4.92 (m, 4H), 7.64 (d, J = 5.02 Hz, 1H), 8.18 (s, 2H),
8.26–8.32 (m, 1H).
1,3-Dinitro-2-[furan-2-yl]propane (2p):10 Yellow crystal, m.p. 34–
1
35 °C; Rf = 0.45 (PE/AcOEt = 4:1); H NMR (400 MHz, CDCl3)
δ 4.43–4.49 (m, 1H), 4.78–4.87 (m, 4H), 6.3–6.31 (m, 1H), 6.36–6.37
(m, 1H), 7.41 (s, 1H).
1,3-Dinitro-2-[thien-2-yl]propane (2q): Reddish-brown crystal,
m.p. 39–40 °C (lit.1 39–41 °C); Rf = 0.50 (PE/AcOEt = 4:1); 1H NMR
(400 MHz, CDCl3) δ 4.61–4.67 (m, 1H), 4.76–4.87 (m, 4H), 7.0–7.02
(m, 2H), 7.31–7.32 (m, 1H).
General procedure
Typically, the reactions were carried out as follows: an oven-dried
Schlenk tube (25 mL) equipped with a magnetic stir bar, was charged
with Ni(PPh3)2I2 (0.3 mmol), P(m-OMePh)3 (0.6 mmol), Zn (2.0 mmol),
Na2CO3 (2.0 mmol) and the aldehyde (0.5 mmol) in CH3NO2 (4 mL).
Then the mixture was stirred at 80 °C under an ambient air atmo-
sphere. After the reaction was completed, the solid catalyst was
filtered off. The filtrate was extracted with ethyl acetate (5 mL×3),
washed with water and brine three times, and then dried with anhy-
drous Na2SO4. The solvent was removed under reduced pressure. The
residue was purified by preparative TLC eluting with petroleum ether/
ethyl acetate, to give the pure 1,3-dinitroalkane.
This work was supported by National Natural Science Founda-
tion of China (20972109).
Received 15 November 2012; accepted 6 January 2013
Paper 1201619 doi: 10.3184/174751913X13596259214753
Published online: 12 March 2013
1,3-Dinitro-2-[4-methoxyphenyl]propane (2a):10 Yellowish crystal,
m.p. 78–80 °C; Rf = 0.54 (PE/AcOEt = 4:1); H NMR (400 MHz,
1
CDCl3) δ 3.80 (s, 3H), 4.24–4.31 (m, 1H), 4.70–4.80 (m, 4H), 6.90 (d,
J = 8.8 Hz, 2H), 7.15 (d, J = 8.8 Hz, 2H).
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1,3-Dinitro-2-[3-methoxyphenyl]propane (2b):19 Yellowish crystal,
1
m.p. 68–70 °C; Rf = 0.54 (PE/AcOEt = 4:1); H NMR (400 MHz,
CDCl3) δ 3.82 (s, 3H), 4.27–4.34 (m, 1H), 4.73–4.82 (m, 4H), 6.77 (s,
1H), 6.81 (d, J = 7.8 Hz, 1H), 6.89 (t, J = 7.3 Hz, 1H), 7.31(m, 1H).
1,3-Dinitro-2-[2-methoxyphenyl]propane (2c):19 Yellowish crystal,
1
m.p. 46–47 °C; Rf = 0.5 (PE/AcOEt = 4:1); H NMR (400 MHz,
CDCl3) δ 3.90 (s, 3H), 4.44–4.51 (m, 1H), 4.87–4.89 (m, 4H), 6.95 (t,
J = 8.3 Hz, 2H), 7.17 (d, J = 8.5 Hz, 1H), 7.34 (m, 1H).
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1,3-Dinitro-2-[3,4-dimethoxyphenyl]propane (2d):16 Yellow crys-
tal, m.p. 64–65 °C; Rf = 0.2 (PE/AcOEt = 4:1); 1H NMR (400 MHz,
CDCl3) δ 3.87 (s, 3H), 3.88 (s, 3H), 4.22–4.30 (m, 1H), 4.72–4.81(m,
4H), 6.72 (d, J = 1.5 Hz, 1H), 6.77 (m, 1H), 6.86 (m, 1H).
1,3-Dinitro-2-[3,4-methylenedioxyphenyl]-propane (2e): Dark yellow
crystal, m.p. 82–84 °C (lit.20 82–84 °C); Rf = 0.33 (PE/AcOEt = 10:1);
1H NMR (400 MHz, CDCl3) δ 4.21–4.29 (m, 1H), 4.69–4.79 (m, 4H),
6.00 (s, 2H), 6.70 (m, 2H), 6.81 (d, J = 8.5 Hz, 1H).
7
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1,3-Dinitro-2-[4-methylphenyl]propane (2f):16 Yellow crystal, m.p.
48–49 °C; Rf = 0.33 (PE/AcOEt = 4:1); 1H NMR (400 MHz, CDCl3)
δ 2.36(s, 3H), 4.26–4.33 (m, 1H), 4.73–4.82 (m, 4H), 7.13 (d, J = 8.03
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1,3-Dinitro-2-[4-hydroxyphenyl]propane (2g):21 Yellowish crystal,
10871.
1
m.p. 96–98 °C; Rf = 0.28 (PE/AcOEt = 4:1); H NMR (400 MHz,
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CDCl3) δ 4.24–4.32 (m, 1H), 4.71–4.81 (m, 4H), 4.98 (s, 1H), 6.85 (d,
J = 8.53 Hz,2H), 7.12 (d, J = 8.53 Hz, 2H).
1,3-Dinitro-2-[2-hydroxyphenyl]propane (2h):11 Dark yellow oil;
1
Rf = 0.34 (PE/AcOEt = 4:1); H NMR (400 MHz, CDCl3) δ 3.90 (s,
3H), 4.41–4.48 (m, 1H), 4.88–4.97 (m, 4H), 6.09(brs, 1H), 6.75–7.22
(m, 4H).
1,3-Dinitro-2-[3-methoxy-4-hydroxyphenyl]propane (2i):Yellowish
crystal, m.p. 85–87 °C, (lit.20 85–88 °C); Rf = 0.30(PE/AcOEt = 4:1);
1H NMR (400 MHz, CDCl3) δ 3.92(s, 3H), 4.23–4.30(m, 1H), 4.72–
4.81 (m, 4H), 6.95–6.99 (m, 2H), 5.70 (brs, 1H), 6.71–6.74(m, 2H),
6.92–6.94(m, 1H).