324 JOURNAL OF CHEMICAL RESEARCH 2007
Isopropyl 3-nitrobenzote (2j): Pale yellow oil (lit.20), δH(400 MHz,
CDCl3), 8.79(s, 1H); 8.34(m, 2H), 7.62(t, J = 7.6 Hz, 1H), 5.27(m,
1H), 1.37(d, J = 6.8 Hz, 6H); υmax/cm-1(NEAT)3084, 2984, 1719,
816, 720.
Experimental
Solvents were dried before using. Chemicals were purchased from
Acros. Melting points were measured on a YANACO melting points
apparatus and were uncorrected. 1H NMR spectra were recorded
with Bruker Avance 400 DMX and 500 DMX spectrometers.
IR spectra were recorded with Nicolet 230 FT-IR spectrometer.
The MS spectrometer was Bruker Esquire 3000 plus. The elemental
analysis apparatus was Eager 200.
Phenylmethyl 3-nitrobenzote (2k): Pale yellow oil (lit.21);
δH(400 MHz, CDCl3), 8.88(s, 1H), 8.42(m, 2H), 7.65(t, J = 7.6 Hz,
1H), 7.43(m, 5H), 5.43(s, 2H); υmax/cm-1(NEAT)3088, 2955, 1723,
820, 716.
Cyclohexyl 3-nitrobenzote (2l): Pale yellow oil; δH(400 MHz,
CDCl3), 8.86(s, 1H), 8.40(m, 2H), 7.66(t, J = 8.0 Hz, 1H), 5.08
Typical procedure for the formation of benzoic ether and its
derivatives.
(m, 1H), 1.99(m, 2H), 1.82(m, 2H), 1.62(m, 4H), 1.49(m, 2H); υmax
/
cm-1(NEAT)3092, 2930, 1727, 774, 712; m/z 248.9(100%, M+);
Anal. Calc. for C13H15NO4: C 62.6, H 6.1, N 5.6. Found: C 62.7,
H 6.1, N 5.8.
Phenylacetonitrile or its derivatives (2 mmol), KI (0.37 g, 2.2 mmol)
and I2(0.05 g, 0.2 mmol) were mixed with the corresponding alcohols
(10 ml). The reaction mixture was then well stirred for the proper time
at an appropriate temperature (illustrated in Table 2). The alcohols
were then removed under vacuum. The mixture was extracted with
ethyl ether or toluene. The organic layer was washed with Na2S2O3
solution (10 ml) and water (2 ¥ 10 ml) and dried over anhydrous
sodium sulfate (Na2SO4). The organic solvent was evaporated.
The residue was purified by column chromatography on silica gel
using ethyl acetate/hexane as eluent.
Methyl 4-chlorobenzoate (2m): Pale yellow solid, m.p. 38–39°C
(lit.,22 39°C); δH(500 MHz, CDCl3), 7.98(d, J = 8.6 Hz, 2H), 7.42(d,
J = 8.6 Hz, 2H), 3.92(s, 3H); υmax/cm-1(NEAT)3059, 2952, 1727, 850.
Methyl benzoate (2n): Colourless oil (lit.1); δH(500 MHz, CDCl3),
8.04(d, J = 8.0 Hz, 2H), 7.55(t, J = 7.6 Hz, 1H), 7.41–7.45(m, 2H),
3.91(s, 3H); υmax/cm-1(NEAT)3034, 2923, 1723.
Received 31 December 2006; accepted 6 June 2007
Paper 06/4357 doi: 10.3184/030823407X218110
Methyl 4-nitrobenzoate (2a): Pale yellow solid, m.p. 93–95°C
(lit.,12 93–94°C); δH(500 MHz, CDCl3), 8.30(d, J = 8.9 Hz, 2H),
8.22(d, J = 8.9 Hz, 2H), 3.99(S, 3H); υmax(KBr)/cm-1(KBr)3079,
2958, 1719, 822.
References
1
2
A.R. Hajipour and G. Mazloumi, Synth. Commun., 2002, 32, 23.
P.L. Anelli, M. Brocchetta, D. Palano and M. Visigalli, Tetrahedron Lett.,
1997, 38, 2367.
Ethyl 4-nitrobenzoate (2b): Pale yellow solid, m.p. 54–56°C(lit.,13
55–57°C); δH(500 MHz, CDCl3), 8.29(d, J = 8.8 Hz, 2H), 8.22
(d, J = 8.8 Hz, 2H), 4.44(q, J = 7.2 Hz, 2H), 1.43(t, J = 7.2 Hz,3H);
υmax(KBr)/cm-1(KBr)3119, 2990, 1717, 841.
3
4
A. Orita, Y. Nagano, J. Hirano and J. Otera, Syn. Lett., 2001, 5, 637.
N.N. Karade, S.G. Shirodkar, B.M. Dhoot and P.B. Waghmare, J. Chem.
Res., 2005, 4, 274.
Propyl 4-nitrobenzoate (2c): Pale yellow solid, m.p. 32–33°C(lit.,14
34°C);δH(500MHz,CDCl3),8.28(d,J=8.8Hz,2H),8.22(d,J=8.9Hz,
2H), 4.34(t, J = 6.6 Hz, 2H), 1.81–1.85(m, 2H), 1.05(t, J = 7.5 Hz,
3H); υmax/cm-1(KBr)3109, 2968, 1719, 874.
5
6
7
8
9
B.R. Travis, M. Sivakumar, G.O. Hollish and B. Borhan, Organic Lett.,
2003, 5, 1031.
S. Antebi, P. Arya, L.E. Manzer and H. Alper, J. Org. Chem., 2002, 67,
6623.
M. Okimoto, Y. Nagata, S. Sueda and Y. Takahashi, Synth. Commun.,
2004, 34, 281.
J.S. Foot, H. Kanno, G.M.P. Giblin and R.J.K. Taylor, Synthesis, 2003, 7,
1055.
Isopropyl 4-nitrobenzoate (2d): Pale yellow solid, m.p. 104–
105°C(lit.,15 104–106°C); δH(500 MHz, CDCl3), 8.28(d, J = 8.9 Hz,
2H), 8.20(d, J = 8.9 Hz, 2H), 5.28–5.30(m, 1H), 1.40(d, J = 6.3 Hz,
6H); υmax/cm-1(KBr)3116, 2923, 1713, 841.
Phenylmethyl 4-nitrobenzoate (2e): Pale yellow solid, m.p. 82–
84°C(lit.,16 83–84°C); δH(500 MHz, CDCl3), 8.28(d, J = 8.9 Hz, 2H),
8.24(d, J = 9.0 Hz, 2H), 7.37–7.46(m, 5H), 5.41(s, 2H); υmax/cm-1
(KBr)3114, 2943, 1713, 845.
N.S. Cho and C.H. Park, Bull. Kor. Chem. Soc., 1994, 15, 924.
10 H. Seto, K. Yoshida, S. Yoshida, T. Shimizu, H. Seki and M. Hoshino,
Tetrahedron Lett., 1996, 37, 4179.
11 M.X. Yu, W.J. Wen and Z.Y. Wang, Synth. Commun., 2006, 36, 2851.
12 J.R. Douglas, G. Patrick, A.B. Jr., G. Anne, C.G. Wayne, R.G. Anne and
D.H. Mark, J. Org. Chem., 1979, 44, 1149.
13 M.A. Brook and T.H. Chan, Synthesis, 1983, 3, 201.
14 H.M. Huang, S.X. Zhu and W.S. Qi, Jilin Daxue Ziran Kexue Xuebao,
1987, 4, 71.
15 T. Shintou, W. Kikuchi and T. Mukaiyama, Bull. Chem. Soc. Jpn., 2003,
76, 1645.
16 J. Barry, G. Bram, G. Decodts, A. Loupy, C. Orange and A. Petit,
Synthesis, 1985, 1, 40.
17 K.E. Fairfull-smith, I.D. Jenkins and W.A. Loughlin, Org. Biomol. Chem.,
2004, 2, 1979.
18 M.M.V. Ramana, S.S. Malik and J.A. Parihar, Tetrahedron Lett., 2004,
45, 8681.
19 J.W. Zhang, Z.L. Xu, H.M. Huang and W. Cheng, Jilin Daxue Ziran
Kexue Xuebao, 1988, 1, 112.
Cyclohexyl 4-nitrobenzote (2f): Pale yellow solid, m.p. 48–49°C
(lit.,17 49–51°C); δH(500 MHz, CDCl3)8.29(d, J = 8.8 Hz, 2H),
8.22(d, J = 8.8 Hz, 2H), 5.06–5.08(m, 1H), 1.97–1.99(m, 2H),
1.80–1.80(m, 2H), 1.58–1.63(m, 4H), 1.46–1.49(m, 2H); υmax/cm-1
(KBr)3114, 2856, 1723, 842.
Methyl 3-nitrobenzote (2g): Pale yellow solid, m.p. 76–78°C(lit.,18
77–78°C); δH(400 MHz, CDCl3), 8.88(s, 1H), 8.37–8.44(m, 2H),
7.66(t, J = 8.0 Hz, 1H), 3.99(s, 3H); υmax/cm-1(KBr)3093, 2960,
1719, 840, 720.
Ethyl 3-nitrobenzote (2h): Pale yellow solid, m.p. 44–45°C(lit.,1
47°C); δH(500 MHz, CDCl3), 8.78(s, 1H), 8.33(m, 2H), 7.62(t,
J = 7.2 Hz, 1H), 4.40(q, J = 7.2 Hz, 2H), 1.39(t, J = 7.2 Hz, 3H);
υmax/cm-1(KBr)3092, 2976, 1723, 841, 712.
20 F.J. Williams, H.M. Relles, J.S. Manello and P.E. Donahue, J. Org. Chem.,
1977, 42, 3419.
21 N.N. Karade, S.G. Shirodkar, R.A. Potrekar and H.N. Karade, Synth.
Commun., 2004, 34, 391.
Propyl 3-nitrobenzote (2i): Pale yellow oil (lit.19), δH(400 MHz,
CDCl3), 8.80(s, 1H); 8.36(m, 2H), 7.65(t, J = 8.0 Hz, 1H), 4.33(t,
J = 7.2 Hz, 2H), 1.83(m, 2H), 1.03(t, J = 7.2 Hz, 3H); υmax/cm-1
(NEAT)3092, 2972, 1723, 816, 716.
22 G.A. Olah, S.C. Narang and A. Garca-Luna, Synthesis, 1981, 10, 790.
PAPER: 07/4357