Subscribe to RSS
DOI: 10.1055/s-2007-970781
A Novel One-Pot Synthesis of Unsymmetrical Acyclic Imides
Publication History
Publication Date:
08 March 2007 (online)
![](https://www.thieme-connect.de/media/synlett/200705/lookinside/thumbnails/10.1055-s-2007-970781-1.jpg)
Abstract
A new and convenient method was found for the one-pot synthesis of symmetrical and unsymmetrical linear imides by reaction of aliphatic and aromatic nitriles with acyclic carboxylic anhydrides in the presence of silica sulfuric acid as an active and recyclable reagent.
Key words
unsymmetrical acyclic imide - silica sulfuric acid - Ritter reaction - nitrile
- 1
Koehn FE.Longley RE.Reed JK. J. Nat. Prod. 1992, 55: 613 - 2
Pettit GR.Kamano Y.Dufresne C.Cerny RL.Herald CL.Schmidt JM. J. Org. Chem. 1989, 54: 6005 - 3
Nakamura H.Iitaka Y.Sakakibara H.Umezawa H. J. Antibiot. 1974, 27: 894 - 4
Nagle DG.Paul VJ.Roberts MA. Tetrahedron Lett. 1996, 37: 6263 - 5
Hargreaves MK.Pritchard JG.Dave HR. Chem. Rev. 1970, 70: 439 -
6a
Davidson D.Skovronek H. J. Am. Chem. Soc. 1958, 80: 376 -
6b
Zil’berman EN. Russ. Chem. Rev. 1960, 29: 331 -
6c
Durrell WS.Young JA.Dresdner RD. J. Org. Chem. 1963, 28: 831 -
6d
Bowser JR.Williams PJ.Kurz K. J. Org. Chem. 1983, 48: 4111 -
7a
Wheeler OH.Rosado O. In The Chemistry of AmidesZabicky J. J. Wiley and Sons; New York: 1970. p.335 -
7b
Challis BC.Challis J. In The Chemistry of AmidesZabicky J. J. Wiley and Sons; New York: 1970. p.759 - 8
Schnyder A.Indolese AF. J. Org. Chem. 2002, 67: 594 - 9
Bates RB.Fletcher FA.Janda KD.Miller WA. J. Org. Chem. 1984, 49: 3038 - 10
Tanaka KI.Yoshifuji S.Nitta Y. Chem. Pharm. Bull. 1987, 35: 364 - 11
Andrus MB.Li W.Keyes RF. Tetrahedron Lett. 1998, 39: 5465 - 12
Lin YI.Lang SA. Synthesis 1980, 119 - 13
Kantlehner W.Fischer P.Kugel W.Moehring E.Bredereck H. Justus Liebigs Ann. Chem. 1978, 512 - 14
Atanasov I.Petrov I.Ognyanova V.Mollov N. Synth. Commun. 1990, 20: 2083 - 15
Yamamoto Y.Onishi S.Azuma Y. Synthesis 1981, 122 - 16
Seiller B.Heins D.Bruneau C.Dixneuf PH. Tetrahedron 1995, 51: 10901 -
17a
Zolfigol MA. Tetrahedron 2001, 57: 9509 -
17b
Salehi P.Dabiri M.Zolfigol MA.Bodaghifard MA. Tetrahedron Lett. 2003, 44: 2889 -
17c
Zolfigol MA.Shirini F.Ghorbani Choghamarani A.Mohammadpoor Baltork I. Green Chem. 2002, 4: 562 -
17d
Salehi P.Dabiri M.Zolfigol MA.Bodaghi Fard MA. J. Braz. Chem. Soc. 2004, 15: 773 -
17e
Salehi P.Dabiri M.Zolfigol MA.Bodaghi Fard MA. Heterocycles 2003, 60: 2435 -
17f
Salehi P.Dabiri M.Zolfigol MA.Baghbanzadeh M. Tetrahedron Lett. 2005, 46: 7051 -
17g
Salehi P.Zolfigol MA.Shirini F.Baghbanzadeh M. Curr. Org. Chem. 2006, 10: 2171 -
18a
Benson FR.Ritter JJ. J. Am. Chem. Soc. 1949, 71: 4128 -
18b
Salehi P.Khodaei MM.Keyvan A. Synth. Commun. 2001, 31: 1947 ; and other references cited therein
References and Notes
General Procedure for Liquid Nitriles
A mixture of 50 mmol of nitrile, silica sulfuric acid (0.18 g, equal to 1.36 mmol H+) and 1 mmol of carboxylic anhydride was heated in a 25 mL round-bottomed flask at 60-70 °C. The reactions were completed within 6-8 h as monitored by TLC (eluent, EtOAc-PE, 1:1). The mixture was filtered and solvent was evaporated under reduced pressure. A solution of NaHCO3 in H2O (1%, 10 mL) was added and the mixture was extracted with Et2O (3 × 25 mL). The organic layer was separated and dried over Na2SO4. When necessary, the crude product was purified by preparative TLC on silica gel.
General Procedure for Solid Nitriles
In a round-bottomed flask the solid nitrile (1 mmol), car-boxylic anhydride (1 mmol) and silica sulfuric acid (0.18 g, equal to 1.36 mmol H+) were mixed thoroughly. The flask was heated at 40-50 °C with concomitant stirring. After completion of the reaction confirmed by TLC (eluent: EtOAc-PE, 1:9), EtOAc (15 mL) was added and filtered. The filtrate was concentrated and purified by preparative TLC.
Spectroscopic Data for Entries 1-16
N-Acetylacetamide (entry 1): white solid, mp 73-74 °C. 1H NMR (300 MHz, CDCl3): δ = 2.07 (s, 6 H), 8.72 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 24.91, 171.96. IR (KBr): 3410, 3265, 3215, 1732 cm-1. MS (EI): m/z (rel. intensity) = 101 (10) [M+], 72 (35), 58 (100).
N-Pentanoylacetamide (entry 2): white solid, mp 62-64 °C. 1H NMR (300 MHz, CDCl3): δ = 0.94 (t, J = 7.3 Hz, 3 H), 1.33-1.45 (m, 2 H), 1.60-1.70 (m, 2 H), 2.38 (s, 3 H), 2.52 (t, J = 7.4 Hz, 2 H), 8.57 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 13.75, 22.17, 25.12, 26.45, 37.03, 172.41, 174.03. IR (KBr): 3260, 3230, 1729 cm-1. MS (EI): m/z (rel. intensity) = 144 (41) [M+], 114 (25), 101 (58), 59 (82), 43 (100).
N-Acetylpropionamide (entry 3): white solid, mp 85-86 °C. 1H NMR (300 MHz, CDCl3): δ = 0.93 (t, J = 7.4 Hz, 3 H), 2.11 (s, 3 H), 2.32 (q, J = 7.4 Hz, 2 H), 8.25 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 8.37, 25.10, 29.69, 30.63, 172.20, 174.63. IR (KBr): 3265, 3236, 1727 cm-1. MS (EI): m/z (rel. intensity) = 115 (50) [M+], 97 (25), 71 (81), 57 (100). Anal. Calcd for C5H9NO2: C, 52.16; H, 7.88; N, 12.17; O, 27.79. Found: C, 52.08; H, 7.79; N, 12.09; O, 27.74.
N-Butyrylpropionamide (entry 4): white solid, mp 109-110 °C. 1H NMR (300 MHz, CDCl3): δ = 0.99 (t, J = 7.4 Hz, 3 H), 1.17 (t, J = 7.4 Hz, 3 H), 1.65-1.73 (m, 2 H), 2.58 (t, J = 7.2 Hz, 2 H), 2.66 (q, J = 7.1 Hz, 2 H), 8.84 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 8.35, 13.62, 17.86, 30.76, 39.27, 174.18, 175.21. IR (KBr): 3260, 3227, 1731 cm-1. MS (EI): m/z (rel. intensity) = 144 (12) [M+], 115 (25), 87 (28), 74 (80), 57 (100).
N-Butyrylisobutyramide (entry 5): white solid, mp 108-109 °C. 1H NMR (300 MHz, CDCl3): δ = 0.72 (t, J = 7.4 Hz, 3 H), 0.95 (d, J = 6.9 Hz, 6 H), 1.37-1.48 (m, 2 H), 2.45 (t, J = 7.4 Hz, 2 H), 2.49-2.56 (m, 1 H), 7.90 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 13.63, 17.72, 18.80, 35.86, 39.32, 175.64, 177.57. IR (KBr): 3260, 3234, 1727 cm-1. MS (EI): m/z (rel. intensity) = 157 (40) [M+], 88 (62), 71(100), 43 (81).
N-Acetyl-2-chloroacetamide (entry 6): white solid, mp 114-115 °C. 1H NMR (300 MHz, CDCl3): δ = 2.43 (s, 3 H), 4.28 (s, 2 H), 8.67 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 24.91, 43.66, 166.83, 171.31. IR (KBr): 3260, 3245, 1740 cm-1. MS (EI): m/z (rel. intensity) = 137 (11) [M + 2], 135 (34) [M+], 93 (20), 43(100).
N-Butyryl-2-chloroacetamide (entry 7): white solid, mp 111-112 °C. 1H NMR (300 MHz, CDCl3): δ = 1.00 (t, J = 7.4 Hz, 3 H), 1.70 (m, 2 H), 2.64 (t, J = 7.3 Hz, 2 H), 4.35 (s, 2 H), 8.51 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 13.54, 17.67, 39.05, 44.11, 167.30, 173.75. IR (KBr): 3255, 3242, 1740 cm-1. MS (EI): m/z (rel. intensity) = 165 (5) [M + 2], 163 (16) [M+], 135 (77), 114 (35), 71 (100), 43 (80).
N-Pentanoyl-2-chloroacetamide (entry 8): white solid, mp 104-105 °C. 1H NMR (300 MHz, CDCl3): δ = 0.95 (t, J = 7.3 Hz, 3 H), 1.34-1.46 (m, 2 H), 1.61-1.71 (m, 2 H), 2.66 (t, J = 7.4 Hz, 2 H), 4.33 (s, 2 H), 8.53 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 13.76, 22.15, 26.22, 36.99, 44.01, 166.97, 173.76. IR (KBr): 3260, 3235, 1739 cm-1. MS (EI): m/z (rel. intensity) = 179 (3) [M + 2], 177 (10) [M+], 135 (30), 107(33), 85 (100), 57 (88). Anal. Calcd for C7H12ClNO2: C, 47.33; H, 6.81; Cl, 19.96; N, 7.89; O, 18.01. Found: C, 47.03; H, 6.77; N, 7.81; O, 17.95.
N-Acetylbenzamide (entry 9): white solid, mp 112-114 °C. 1H NMR (300 MHz, CDCl3): δ = 2.39 (s, 3 H), 7.21-7.63 (m, 5 H), 8.44 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 25.47, 127.58, 129.08, 132.72, 133.30, 165.53, 173.15. IR (KBr): 3295, 1722 cm-1. MS (EI): m/z (rel. intensity) = 163 (10) [M+], 105 (100), 77 (78).
N-Acetyl-4-methylbenzamide (entry 10): white solid, mp 103-104 °C. 1H NMR (300 MHz, CDCl3): d = 2.45 (s, 3 H), 2.63 (s, 3 H), 7.32 (d, J = 8.0 Hz, 2 H), 7.75 (d, J = 8.2 Hz, 2 H), 8.59 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 21.59, 25.65, 127.93, 129.58, 129.80, 144.08, 165.84, 174.10. IR (KBr): 3395, 3285, 1709 cm-1. MS (EI): m/z (rel. inten-sity) = 177 (25) [M+], 162 (30), 119 (100), 91 (80), 65 (52). Anal. Calcd for C10H11NO2: C, 67.78; H, 6.26; N, 7.9; O, 18.06. Found: C, 67.62; H, 5.83; N, 8.00; O, 18.54.
N-Butyryl-4-methylbenzamide (entry 11): white solid, mp 87-88 °C. 1H NMR (300 MHz, CDCl3): δ = 1.04 (t, J = 7.3 Hz, 3 H), 1.73-1.82 (m, 2 H), 2.44 (s, 3 H), 7.31 (d, J = 8.0 Hz, 2 H), 7.76 (d, J = 8.0 Hz, 2 H), 8.64 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 13.74, 17.59, 21.59, 39.42, 127.69, 129.65, 130.00, 144.05, 165.37, 176.24. IR (KBr): 3270, 2950, 2935, 1710 cm-1. MS (EI): m/z (rel. intensity) = 205(32) [M+], 136 (20), 119 (100), 91 (33). Anal. Calcd for C12H15NO2: C, 70.22; H, 7.37; N, 6.82; O, 15.59. Found: C, 69.95; H, 7.01; N, 6.79; O, 15.52.
N-Pentanoyl-4-methylbenzamide (entry 12): white solid, mp 101-102 °C. 1H NMR (300 MHz, CDCl3): δ = 0.97 (t, J = 7.3 Hz, 3 H), 1.38-1.48 (m, 2 H), 1.66-1.76 (m, 2 H), 2.44 (s, 3 H), 3.02 (t, J = 7.5 Hz, 2 H), 7.31 (d, J = 7.9 Hz, 2 H), 7.79 (d, J = 8.2 Hz, 2 H), 8.53 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 13.89, 21.59, 22.32, 26.27, 37.30, 127.73, 129.65, 130.04, 144.04, 165.40, 176.46. IR (KBr): 3280, 2920, 2924, 1699 cm-1. MS (EI): m/z (rel. intensity) = 219 (34) [M+], 136 (20), 119 (100), 91 (50).
N-Acetyl-4-nitrobenzamide (entry 13): white solid, mp 118 °C. 1H NMR (300 MHz, CDCl3): δ = 2.33 (s, 3 H), 4.07 (s, 2 H), 7.47 (d, J = 8.5 Hz, 2 H), 8.1 (br s, 1 H), 8.23 (d, J = 8.6 Hz, 2 H). 13C NMR (75 MHz, CDCl3): δ = 25.08, 41.06, 124.00, 130.57, 140.63, 147.33, 170.66, 171.98. IR (KBr): 3435, 3250, 2990, 1732 cm-1. MS (EI): m/z (rel. intensity) = 222 (11) [M+], 163 (88), 137 (30), 43 (100). Anal. Calcd for C10H10N2O4: C, 54.05; H, 4.54; N, 12.61; O, 28.80. Found: C, 54.02; H, 4.50; N, 12.55; O, 28.77.
N-Butyryl-4-nitrobenzamide (entry 14): white solid, mp 122 °C. 1H NMR (300 MHz, CDCl3): δ = 0.99 (t, J = 7.4 Hz, 3 H), 1.64-1.74 (m, 2 H), 2.50 (t, J = 7.3 Hz, 2 H), 4.16 (s, 2 H) 7.47 (d, J = 8.8 Hz, 2 H), 8.09 (br s, 1 H), 8.22 (d, J = 8.8 Hz, 2 H). 13C NMR (75 MHz, CDCl3): δ = 13.56, 17.80, 39.30, 43.51, 123.74, 130.60, 140.87, 147.27, 171.25, 174.20. IR (KBr): 3205, 3000, 1729 cm-1. MS (EI): m/z (rel. intensity) = 250 (10) [M+], 180 (30), 163 (50), 133 (25), 88 (50), 71 (100), 43 (75).
N-Acetyl-3-chlorobenzamide (entry 15): white solid, mp 105-107 °C. 1H NMR (300 MHz, CDCl3): δ = 2.63 (s, 3 H), 7.45-7.49 (m, 3 H), 7.88 (s, 1 H), 8.71 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 25.65, 125.75, 128.24, 130.23, 133.24, 134.41, 135.27, 164.63, 173.81. IR (KBr): 3418, 3196, 1718 cm-1. MS (EI): m/z (rel. intensity) = 199 (8) [M + 2], 197 (16) [M+], 168 (18), 139 (100), 111 (25), 75 (20), 71 (100), 43 (50).
N-Butyryl-3-chlorobenzamide (entry 16): white solid, mp 97-100 °C. 1H NMR (300 MHz, CDCl3): δ = 1.04 (t, J = 7.4 Hz, 3 H), 1.73-1.80 (m, 2 H), 2.98 (t, J = 7.4 Hz, 2 H), 7.44-7.73 (m, 3 H), 7.87 (s, 1 H), 8.54 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 13.71, 17.46, 39.58, 125.87, 128.22, 129.78, 130.16, 133.13, 133.50, 134.59, 135.20, 164.55, 176.88. IR (KBr): 3420, 3185, 2920, 1710 cm-1. MS (EI): m/z (rel. intensity) = 227 (2) [M + 2], 225 (7) [M+], 196 (30), 156 (75), 139 (100), 111 (75), 75 (50), 43 (88).