10852
A.V. Messorosh et al. / Tetrahedron 64 (2008) 10849–10852
3.2.8. 2-Chloro-3-cyclohexyl-N-phenylmaleimide (17)
1642, 1352, 1255, 1084, 927 cmꢂ1
; dH (300 MHz, CDCl3) 2.58 (2H, t, J
7.5 Hz, C]C–CH2), 1.66 (2H, quint, J 7.5 Hz, C]C–CH2CH2), 1.43–
1.28 (6H, m, CH2), 0.91 (3H, t, J 6.5 Hz, CH3); dC (75 MHz, CDCl3)
163.2, 160.2, 145.0, 136.2, 31.6, 29.4, 27.1, 25.1, 22.8, 14.3.
Pale yellow solid (810 mg, 70%); mp 89–91 ꢀC (cyclohexane).
[Found: C, 66.2; H, 5.4; N, 4.7. C16H16ClNO2 requires C, 66.32; H,
5.53; N, 4.84%.] nmax (KBr) 3700–3300 (br), 3066, 2950–2800 (br),
1800–1550 (br), 1506, 1401, 1201, 1140, 1118, 943 cmꢂ1
; dH
(300 MHz, CDCl3) 7.53–7.33 (5H, m, Ph), 2.84 (1H, tt, J 3.9, 11.4 Hz,
CH), 1.95–1.73 (7H, m, CH2), 1.43–1.31 (3H, m, CH2); dC (75 MHz,
CDCl3) 168.0, 164.7, 144.3, 132.8, 131.7, 129.5, 128.4, 126.3, 36.2, 29.8,
26.5, 25.9; m/z (EI, 70 eV) 291 (32 Mþ), 289 (100 Mþ), 254 (50), 236
(10), 234 (28), 223 (40), 221 (100), 77 (60%).
3.4.2. 2-Chloro-3-ethylmaleic anhydride (16)
Colourless oil (320 mg, 33%). [Found: C, 45.2; H, 3.4. C6H5ClO3
requires C, 44.86; H, 3.12%.] nmax (KBr) 3700–3300 (br), 1795,
1284, 927 cmꢂ1
; dH (300 MHz, CDCl3) 2.61 (2H, q, J 7.5 Hz, CH2),
1.27 (3H, t, J 7.5 Hz, CH3); dC (75 MHz, CDCl3) 163.0, 160.3, 145.8,
135.9, 18.7, 11.4.
3.2.9. 2,3-Dicyclohexyl-N-phenylmaleimide (18)
Pale yellow thick oil (400 mg, 30%). [Found: C, 78.1; H, 7.7; N, 4.3.
C22H27NO2 requires C, 78.34; H, 8.01; N, 4.15%.] nmax (KBr) 3700–
3.5. One-pot synthesis of 2-cyclohexyl-3-(1,4-dioxan-2-yl)-
maleic anhydride (11) (method D)
3300 (br), 2928, 2853, 1707, 1600, 1501, 1450, 1384, 1116 cmꢂ1
; dH
(300 MHz, CDCl3) 7.55–7.34 (5H, m, Ph), 2.77 (2H, tt, J 3.5, 12.0 Hz,
CH), 1.98–1.62 (14H, m, CH2), 1.42–1.27 (6H, m, CH2); dC (75 MHz,
CDCl3) 170.5, 144.1, 134.2, 130.6, 129.2, 126.3, 36.6, 31.0, 26.8, 26.1.
A mixture of 2,3-dichloromaleic anhydride (0.5 g, 3 mmol)
and benzoyl peroxide (15 mg, 0.06 mmol) was heated in a flask
equipped with a reflux condenser for 1.5 h. The solvent was re-
moved under reduced pressure and 1,4-dioxane (10 ml) was added.
An additional benzoyl peroxide (70 mg, 0.3 mmol) was added and
mixture was heated to reflux for 1 h. This operation was repeated
six times. Product was isolated by column chromatography as
described in method A to give 11 (420 mg, 52%) as a viscous
yellowish oil. [Found: C, 62.8; H, 6.5. C14H22O5 requires C,
63.16; H, 6.77%.] nmax (KBr) 3700–2700 (br), 1800–1700 (br),
3.2.10. 2-Benzyl-3-chloro-N-phenylmaleimide (19)
Yellow solid (620 mg, 52%); mp 105–107 ꢀC (hexane). [Found: C,
68.4; H, 4.1; N, 4.5. C17H12ClNO2 requires C, 68.57; H, 4.03; N, 4.71%.]
nmax (KBr) 3700–3300 (br), 1720, 1651, 1598, 1493, 1383, 1113 cmꢂ1
;
dH (300 MHz, CDCl3) 7.53–7.27 (10H, m, Ph), 3.92 (2H, s, CH2); dC
(75 MHz, CDCl3) 168.0, 164.5, 139.8, 135.7, 134.5, 131.6, 129.62,
129.58, 129.4, 128.5, 127.8, 126.3, 30.4.
1630, 1400–1200 (br), 1082, 927 cmꢂ1
; dH (300 MHz, CDCl3)
4.73 (1H, dd, J 3.0, 10.2 Hz, CHdiox); 3.89–3.70 (5H, m, CH2diox),
3.57 (1H, dd, J 10.2, 11.4 Hz, O–CHaHeCH–O), 3.11 (1H, tt, J 3.6,
11.7 Hz, CHc-Hex), 1.92–1.58 (7H, m, CH2c-Hex), 1.36–1.22 (3H, m,
CH2c-Hex); dC (75 MHz, CDCl3) 164.5, 164.4, 152.5, 137.7, 71.6,
69.4, 67.3, 66.7, 37.0, 30.6, 30.3, 26.4, 26.3, 25.7; m/z (EI, 70 eV)
266 (93 Mþ), 238 (20), 236 (20), 222 (26), 204 (100), 176 (60),
134 (73%).
3.3. 2-Chloro-3-(1,1,2-trimethylpropyl)-maleic anhydride
(14b) (method B)
A mixture of 2,3-dichloromaleic anhydride (500 mg, 3 mmol),
benzoyl peroxide (150 mg, 0.6 mmol), 2,3-dimethylbutane (2 ml),
an acetonitrile solution of HCl ([HCl]¼2.7 M, 2 ml) and benzene
(6 ml) was heated for 2 h at 80 ꢀC in a sealed tube. An additional
portion of benzoyl peroxide (75 mg, 0.3 mmol) was added, and the
mixture was heated for 1 h more. The progress of the reaction was
monitored by GLC. The product was isolated by column chroma-
tography analogous to method A. Removal of the solvent gave 14b
(510 mg, 78%) as a colourless oil with 97% purity (GLC). [Found: C,
55.1; H, 5.8. C10H13ClO3 requires C, 55.43; H, 6.00%.] nmax (KBr)
References and notes
1. (a) De Lucchi, O.; Modena, G. Tetrahedron 1984, 40, 2285; (b) Kar, A.; Gogoi, S.;
Argade, N. P. Tetrahedron 2005, 61, 5297; (c) Gogoi, S.; Argade, N. P. Tetrahedron
2006, 62, 2715.
2. (a) Weidenmu¨ller, H.-L.; Cavagna, F.; Fehlhaber, H.-W.; Pra¨ve, P. Tetrahedron Lett.
1972, 13, 3519; (b) Weber, W.; Semar, M.; Anke, T.; Bross, M.; Steglich, W. Planta
Med. 1992, 58, 56; (c) Mondal, G.; Dureja, P.; Sen, B. Indian J. Exp. Biol. 2000, 38,
84; (d) Nakamura, N.; Hirakawa, A.; Gao, J.-J.; Kakuda, H.; Shiro, M.; Komatsu,
Y.; Sheu, C.; Hattori, M. J. Nat. Prod. 2004, 67, 46.
3700–3300 (br), 2968, 1836, 1775, 1610, 1467, 1250, 1139, 930 cmꢂ1
;
dH (300 MHz, CDCl3) 2.34 (1H, sept, J 6.9 Hz, CHMe2), 1.40 (6H, s,
CMe2), 0.88 (6H, d, J 6.9 Hz, CHMe2); dC (75 MHz, CDCl3) 162.4,
160.6, 149.5, 135.2, 42.3, 34.9, 22.9, 17.9.
3. Chen, X.; Zheng, Y.; Shen, Y. Chem. Rev. 2007, 107, 1777.
4. (a) Kar, A.; Argade, N. P. J. Org. Chem. 2002, 67, 7131; (b) Kar, A.; Argade, N. P.
Tetrahedron 2003, 59, 2991.
3.4. Alkylallylsulphones as the source of radicals (method C)
5. (a) Dubernet, M.; Caubert, V.; Guillard, J.; Viaud-Massuard, M.-C. Tetrahedron
2005, 61, 4585; (b) Stewart, S. G.; Polomska, M. E.; Lim, R. W. Tetrahedron Lett.
2007, 48, 2241.
6. (a) Ratemi, E. S.; Dolence, J. M.; Poulter, C. D.; Vederas, J. C. J. Org. Chem. 1996, 61,
6296; (b) Adlington, R. M.; Baldwin, J. E.; Cox, R. J.; Pritchard, G. J. Synlett 2002,
A
mixture of 2,3-dichloromaleic anhydride (1 g, 6 mmol),
corresponding alkylallylsulphone (3 mmol), tert-butyl peroxide
(60 mg, 0.4 mmol) and chlorobenzene (10 ml) was refluxed in
a flask equipped with a reflux condenser for 2 h. An additional
alkylallylsulphone (1.5 mmol) and tert-butyl peroxide (60 mg,
0.4 mmol) were added and reflux was continued for additional
2 h. The last operation was repeated once more. Products were
isolated by column chromatography as described in method A.
`
820; (c) Selles, P. Org. Lett. 2005, 7, 605.
7. Denance, M.; Banaszak, E.; Samadi, M. Tetrahedron Lett. 2006, 47, 7409.
8. (a) Schmerling. L. U.S. Patent 3,780,066, 1973; (b) Stahlke, K. -R., Hartmann, W.
German Patent 2,352,216, 1975; (c) Araneo, S.; Arrigoni, R.; Bjørsvik, H.-R.;
Fontana, F.; Liguori, L.; Minisci, F.; Recupero, F. Tetrahedron Lett. 1996, 37, 6897.
9. Trukhin, A. V.; Messorosh, A. V.; Karavan, V. S.; Eliseenkov, E. V. Russ. J. Org.
Chem. 2007, 43, 801.
10. Russell, G. A. J. Am. Chem. Soc. 1958, 80, 4987.
3.4.1. 2-Chloro-3-hexylmaleic anhydride (15)
Colourless oil (450 mg, 35%). [Found: C, 55.5; H, 6.1. C10H13ClO3
requires C, 55.43; H, 6.00%.] nmax (KBr) 3700–3300 (br), 2938, 1770,
11. Quiclet-Sire, B.; Zard, S. Z. J. Am. Chem. Soc. 1996, 118, 1209.
12. Watson, W. H.; Wu, G.; Richmond, M. G. J. Chem. Crystallogr. 2003, 33, 983.
13. Relles, H. M. J. Org. Chem. 1972, 37, 3630.