658 JOURNAL OF CHEMICAL RESEARCH 2011
N-ethylsuccinimide (2f): Colourless oil, 1H NMR (400 MHz,
CD3OD): δ = 0.93–0.97 (3H, m), 2.53 (4H, s, 2COCH2), 3.31–3.36
(2H, m, NCH2); 13C NMR (100 MHz, CD3OD): δ = 177.04 (2C=O),
33.42, 28.04 and 12.74.
these oxidation reactions afforded N-substituted cyclic imides
2e–i in good yields. The very sterically hindered N-tert-butyl-
4-hydroxybutanamide 1j gave no detectable cyclic imides.
Various cyclic imides were obtained in moderate to good yields
(69–85%) using the method, which were similar or a bit better
than the yields (14–88%) obtained by traditional methods.6–12
In conclusion, we have reported a mild and facile method
for synthesis of cyclic imides by oxidative cyclisation of
hydroxy amides with PCC under ultrasonic irradiation.
In addition, a wide variety of cyclic imides were obtained in
moderate to good yields with the method. The synthetic method
has several advantages compared to the previous methods
including mild conditions, simplified work-ups and low
cost.
N-propylsuccinimide (2g): Colourless oil, 1H NMR (400 MHz,
CD3Cl): δ = 0.60–0.63 (3H, m), 1.25–1.34 (2H, m), 2.44 (4H, s,
2COCH2), 3.14–3.17 (2H, m, NCH2). 13C NMR (100 MHz, CD3Cl):
δ = 177.18 (2C=O), 39.94, 27.89, 20.70 and 10.94.
N-isopropylsuccinimide (2h): White solid, m.p. 95–96 °C (lit.20
95–97 °C). 1H NMR (400 MHz, CD3Cl): δ = 1.36 and 1.37 (6H, 2s),
2.63 (4H, s, 2COCH2), 4.33–4.40 (1H, m, NCH). 13C NMR (100 MHz,
CD3Cl): δ = 177.17 (2C=O), 43.69, 28.05 and 19.11.
N-benzylsuccinimide (2i): White solid, m.p. 102–103 °C (lit.21 104–
1
105 °C). H NMR (400 MHz, CD3Cl): δ = 2.63 (4H, s, 2COCH2),
4.61 (2H, s, NCH2), 7.24–7.37 (5H, m, 5 CH of benzene). 13C NMR
(100 MHz, CD3Cl): δ = 176.84 (2C=O), 135.90, 128.78, 128.57,
127.86 (6 C benzene), 42.30 and 28.18.
Experimental
Reagents and solvents were obtained from commercial suppliers. All
reactions were carried out under air and monitored by TLC using
commercial aluminum-backed silica gel plates. The ultrasonic reac-
tions were performed in ultrasonic cleaner (KQ5200DE, 70W) with
frequency of 40 MHz. Melting points were observed on YRT-3 Melt-
ing Point Tester and are uncorrected. NMR spectra were recorded on
Varian Inova-400/500 MHz NMR spectrometer with TMS as an inter-
nal reference. MS were recorded on a LCQ Advanted MAX mass
spectrometer. Silica gel (200–300 mesh) was used for the oxidation
reactions and column chromatography.
Received 1 October 2011; accepted 25 October 2011
Paper 1100914 doi: 10.3184/174751911X13202290249578
Published online: 22 November 2011
References
1
2
J. Bauer and J. Rademann, Tetrahedron Lett., 2003, 44, 5019.
S.E. Mallakpour, A.R. Hajipour and S. Habibi, Eur. Polym. J., 2001, 37,
2435.
3
4
S.E. Mallakpour, A.R. Hajipour, K. Faghihi, N. Foroughifar and J. Bagheri,
J. Appl. Polym. Sci., 2001, 80, 2416.
C.W. Struijk, A.B. Sieval, J.E. Dakhorst, M. van Dijk, P. Kimkes, R.B.
Koehorst, H. Donker, T.J. Schaafsma, S.J. Picken, A.M. Van de Craats,
J.M. Warman and H. Zuilhof, J. Am. Chem. Soc., 2000, 122, 11057.
P.Y. Reddy, S. Kondo, T. Toru and Y.Ueno, J. Org. Chem., 1997, 62, 2652.
A. Da Settimo, G. Primofiore, F. Da Settimo, F. Simorini, C. La Motta,
A. Martinelli and E. Boldrini, Eur. J. Med. Chem., 1996, 31, 49.
N.B. Mehta, A.P. Phillips, F.F. Lui and R.E. Brooks, J. Org. Chem., 1960,
25, 1012.
General procedure
Hydroxyl amides (1a–j) were obtained by the reactions of lactones
with ammonia or amine in MeOH at room temperature.17 The prepara-
tion of cyclic imides (2a–j): A magnetically stirred hydroxyl-
terminated amides (20 mmol) was added to a homogeneous mixture
of PCC (60 mmol) and silica gel (same weight as PCC) in CH2Cl2
(200 mL), and the reaction was stirred for 2 h at room temperature
with ultrasonic irradiation. The reaction mixture was then filtered
through a pad of silica gel column using CH2Cl2 as the eluent. The
solvent was evaporated and the residue was purified on a silica gel
column using PE−EtOAc (1:3) as the eluent furnished cyclic imides.
Succinimide (2a): White solid, m.p. 124–127 °C (lit.18 125–127 °C).
1H NMR (500 MHz, CD3Cl): δ = 2.76 (4H, s, 2COCH2), 8.88 (1H, s,
NHCO). 13C NMR (125 MHz, CD3Cl): δ = 178.15 (2C=O) and
29.82.
5
6
7
8
9
M.L. Pedersen and D.B. Berkowitz, J. Org. Chem., 1993, 58, 6966.
L.R. Domingo and M.J. Aurell, M. Arno, Tetrahedron, 2009, 65, 3432.
10 S. Inoue, H. Shiota, Y. Fukumoto and N. Chatani, J. Am. Chem. Soc., 2009,
131, 6898.
11 J. Zhang, M. Senthilkumar, S.C. Ghosh and S.H. Hong, Angew. Chem. Int.
Ed., 2010, 49, 6391.
12 S.V. Pronin and S.A. Kozmin, J. Am. Chem. Soc., 2010, 132, 14394.
13 K. Wietzerbin, J. Bernadou and B. Meunier, Eur. J. Org. Chem., 2000,
1391.
Glutarmide (2b): White solid, m.p. 149–151 °C (lit.18 154–157 °C).
1H NMR (500 MHz, CDCl3): δ = 1.98–2.04 (m, 2H), 2.58–2.61 (m,
4H, 2COCH2), 8.30 (s, 1H, NHCO). 13C NMR (125 MHz, CDCl3):
δ = 172.94 (2C=O), 31.86 and 18.09. MS (m/z, %): 114.1 (M++1).
Adipimide (2c): White solid, m.p. 161–163 °C (lit.18 167–172 °C).
1H NMR (500 MHz, CD3OD): δ = 1.91 (4H, s), 2.75 (4H, s, 2COCH2).
13C NMR (125 MHz, CD3OD): δ = 176.30 (2C=O), 34.22 and 20.13.
N-methylsuccinimide (2e): White solid, m.p. 67–68 °C (lit.19 70–
71 °C). 1H NMR (400 MHz, CD3Cl): δ = 2.68 (4H, s, 2COCH2), 2.95
(3H, s, NCH3). 13C NMR (100 MHz, CD3OD): δ = 177.21 (2C=O),
28.16 and 24.69.
14 G. Buchi and B.Egger, J. Org. Chem., 1971, 36, 2021.
15 J.H. Tumlinson, D.D. Hardee, R.C. Gueldner, A.C. Thompson, P.A. Hedin
and J.P. Minyard, Science, 1969, 166, 1010.
16 L.L. Adams and F.A. Luzzio, J. Org. Chem., 1989, 54, 5387.
17 P.A. Zoretic, P. Soja and T. Shiah, J. Med. Chem., 1978, 21, 1330.
18 A.A. Taherpour, and M. Hamid. Turk. J. Chem., 2005, 29, 317.
19 A.A. Taherpour, A. Abramian and H.Kardanyazd, Chin. J. Org. Chem.,
2007, 27, 123.
20 G. Tsolomiti, K. Tsolomiti, and A. Tsolomitis, Heterocycl. Commun.,
2006, 12, 179.
21 K. Adeppa, D.C. Rupainwar and K.Misra, Proc. Natl. Acad. Sci. India,
Sect. B, Biol. Sci., 2010, 80, 30.