A Novel One-Pot Synthesis of Unsymmetrical Acyclic Imides

Zohreh Habibi; Peyman Salehi; Mohammad Ali Zolfigol; Maryam Yousefi

doi:10.1055/s-2007-970781

LETTER

A Novel One-Pot Synthesis of Unsymmetrical Acyclic Imides

Zohreh Habibi^a, Peyman Salehi*^b, Mohammad Ali Zolfigol^c, Maryam Yousefi^a
^a Department of Chemistry, Shahid Beheshti University, Evin, Tehran 19839-63113, Iran
^b Department of Phytochemistry, Medicinal Plants and Drugs Research Institute, Shahid Beheshti University, PO Box 19835-389, Evin, Tehran, Iran
Fax: +98(21)22431783; e-Mail: p-salehi@sbu.ac.ir;
^c Department of Chemistry, Faculty of Science, Bu-Ali Sina University, Hamadan 65174, Iran

Abstract

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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

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Referenzen

References and Notes

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6d Bowser JR. Williams PJ. Kurz K. J. Org. Chem. 1983, 48: 4111

7a Wheeler OH. Rosado O. In The Chemistry of Amides Zabicky J. J. Wiley and Sons; New York: 1970. p.335

7b Challis BC. Challis J. In The Chemistry of Amides Zabicky J. J. Wiley and Sons; New York: 1970. p.759

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17a Zolfigol MA. Tetrahedron 2001, 57: 9509

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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

19

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.

20

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).