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Note Selective Conversion of Nitriles to Amides by Amberlyst A-26 Supported Hydroperoxide

Note Selective Conversion of Nitriles to Amides by Amberlyst A-26 Supported Hydroperoxide

Indian 10umal of Chemistry Vol. 38B, August 1999, pp. 974-975

Note

Selective conversion of to by line, we wish to report herein a mild, efficient and Amberlyst A-26 supported selective method for the conversion of nitriles to amjdes with (35 %) in the presence M Mansour Lakouraj* & K Bahrami of catalytic amount of AmberIyst A-26 (OH- form). Department of Chemistry The representative examples illustrating the Razi University Kermanshah 67149,Iran usefulness of this method are listed in Table I. Using Received 25 September 1998; accepted (revised) 15 June /999 this method, aliphatic as we ll as aromatic nitriles are converted to the corresponding ami des in high yields. A mild, efficient and selective conversion of nitriles to ex, ~-Unsaturated , acrylonitrile, is converted to am ides is achieved by employing Amberlyst A-26 supported hydroperoxide, which is prepared in situ from the corresponding epoxy (entry 9, Table I). and Amberlyst A-26 (OH- form). Entries 10 and I I (Table I) demonstrate the Nitriles and dinitriles are transformed to their selectivity of the method in which ethoxy carbonyl corresponding amides and diamides, respectively. and amide groups remained unchanged during the Reacti ons proceed within 0.5-5 hr upon addition of a reaction. In th e case of dinitri les (entries 12-14, catalytic amount of Amberlyst A 26(OH-) to a methanolic Table I), their corresponding diamides are obtained soluti on of nitrile and hydrogen peroxide (35%), at room as the sole products. te mperature The reactions proceed within 0.5-5 hI' upon Nitriles may be hydrolyzed to give either amides or addition of the resin to a solution of substrate and carboxylic acids. The selective conversion of nitriles hydrogen peroxide in methanol , at room temperature. to amides is difficult, because the product is often Some advantages of thi s method inc lude: mild more easily hydrolyzed than the nitrile from which it reaction condition, convenient product isolation by l was formed . Several methods have been reported to means of simple filtration and evaporation, no further carry out this transformation, e.g. the traditional hydrolysis to the corresponding acid and recycling of methods such as acid 2 or base' catalyzed hydrolysis, the resin. 4 alkaline hydrogen peroxide , sodium peroxide in 6 Experimental Section DMS0 5, metal catalyzed hydration , aqueous sodium 7 perborate , TiCI4 in acetic acids, Mn02/SiO/, AmberIyst A-26 ( OH- form ) is either purchased catalyzed and uncatalyzed AbO, IO, from MERCK company or prepared by simple ll l2 IH20 2/carbonate , dimethyl , etc. exchange reaction of chloride form of the resin with In general, each of these procedures suffer from at 1.0 N NaOH aqueous solution. least one of the following drawbacks: strong acidic or General procedure for conversion of nitriles to basic media, low to moderate yield, severe reaction amides. To a solution of nitrile ( 1.0 mmo le) and condition causing the oxidation or hydrolysis of other hydrogen peroxide (35%, 4 mmo les) in meth anoi functional groups on the substrate, long reaction time, (5mL); AmberIyst A-26 (1 . 1g of wet 01-( form) was further hydrolysis to the corresponding carboxylic added. After a few minutes, th e mixture was stirred at acid and tedious product isoiation. Therefore, there room temperature and the progress of the reaction was still exists a need for simple, mild and selective monitored on T L C ( eluent; n-hexane/ethe r: 21 I). On methods for the efficient conversion of nitriles to completion of reaction, methanol or acetonitri Ie amides. (5 mL) was added to the reaction mixture and then Polymer supported reagents and catalysts, filtered. Evaporation of th e filtrate afforded the pure especially the anion exchange resin s have been widely amide. Identification and analysis of the products l appli ed fo r organic transformations '. Their main were made on the basis of IR, IH NMR spectra and advantage over monomeric reagent is their phys ical data compared with those o /" th e au thenti c insolubility in the reacti on media and consequently samples. Entry No. 13, m. p. l70°C; Anal. Calcd. fo r the easier work-up of the reaction mixture. Along this C9Hl sN202: C, 58; H, 9.7; N, 15 . Found: C, 57.9; H, NOTES 975

Table I· Conversion of nitrile to amide with Amberlyst A- 26/ H20 2 :I Entry Substrate Product Time Yield (Lit. 14 m.p.) No. (hr) (%) °C benzonitrile benzamide 0.8 98 125( 128-29) 2 m-bromobenzonitrile m -bromobenzamide 0.6 96 154(155 ) 3 m-aminobenzonitrile m-aminobenzamide 1.7 95 I 15( I 15- 16) 4 p-aminobenzonitrile p-aminobenzamide 3 97 I 80( 18 1-83) 5 p-nitrobenzonitrile p-nitrobenzamide 0.5 99 200( 199-20 I) 6 acetonitrile acetamide 1.5 97 80(79-8 1) 7 chloroacetonitrile chloroacetamide 2 93 I 16( I I 6- I 8) 8 phenylacetonitrile phenylacetamide 5 86 154(155-56) 9 acrylonitrile 4 76 oil y (32-34) 10 ethoxycyanoacetate Carboxyethylacetamide 4 90 46(50) II cyanoacetamide Malimide 4 85 168( 170) 12 I ,6- dicyanohexane 1,6-hexanedicarboxamide 0.75 96 218(2 17) 13 1,7- dicyanoheptane 1,7-heptanedicarboxamide 1.5 95 170(172) 14 I,IO-dicyanodecane I ,I O-decanedicarboxamide 5 92 188( 189) :~/roN~ 15 ::o=r~ 1.5 99 15 1-53

(a) All reactions are carri ed out in methanol with substrate / H20 2 / A-26 ratio being 1/4/0.1

9.8; N, 14.7%. Entry No. 14, m. p. 188-89°C; Anal. (c) Creaves P M, Landor P D, Landor S R & Odyck 0 , Calcd for CI 2H24N20 2 : C, 63.1; H, 10.6; N, 12.27. Tetrahedron Letl, 3, 1973,209 . Found: C, 63.0; H, 10.4; N, 12%. Entry No. 15 , m. p. 5 Kornblum N & Singaram S, J Org Chem, 44, 1979, 4727 . 6 (a) Breslow R, Fairweather R & Keana J, JAm Chem Soc, 89, lSI-53°C; Anal. Calcd for C!lH1JNOJ: C, 63.7; H, 1967, 2135. 6.3; N, 6.7. Found: C, 63.6; H, 6.4; N, 6.5%. (b) Buckingham D A, Keene F R & Sargeson A M. J Am Chem Soc, 95, 1973,5649. Acknowledgement 7 Reed K L, Gupton J T & Solarz T J, S.1'llth COmmltll, 20, 1990, Authors are thankful to Prof. B Tamami of Shiraz 563. University, and grateful to Razi University Research 8 Mukaiyama T, Kamio K, Kobayashi S & Takei H. Chem Lell, 1973,357 . Council for partial support to this work. 9 Breuilles P, Leclerc R & Uguen D, TetrahedrOlI Lell. 35, 1994, 1401 . References 10 Wilgus C P, Downing S, Molitor E. Bains S. Pagni R M & (a) March J, Advanced Orgallic Chemistry, 3 rd edn, (Wiley­ Kabalka G W, Tetrahedron Lett, 36, 1995,3469. Interscience, New York), 1985, p 788. II Balicki R & Kaczmarek L, S)'lIth C OIIIIIIIIII 23 . 1993,3 149. (b) Sehaefer F C, in The Chemistry of Cyano Group, edited by 12 Bose D S & Baquer S M, SYllth COIIIIIIIIII. 27, 1997. 3119 . Z Rappaport (Interscience, New YorK), 1970, p 239 . 13 Sherrington D C & Hodge P, SYllthesis alld S{'/I[I/"{/tioll Usillg 2 (a) Johnson H E & Crosby D G, J Org Chem, 27,1962,798. Functional Polymers, (John Wiley & Sons. England ), 1988. (b) Becke F, Fleig H & PassIer, Liebig"s Anll Chem, 749, p 43. 1971, 198 . 3 Hall J H & Gisler M, J Org Chem, 41,1976,3769. 14 Fluka Catalogue, Chemicals alld Biochelllicais. (1993-94). 4 (a) Mc master L & Noller C R, J Indiall Chem Soc, 12, 1935, Bukingham J, DictiollQl:V of Organic Compound.I·, Vol 5, 652. (Chapman & Hall), 1982. (b) McIsaac J E, Ball R E & Behrman E J, J Org Chem, 36, (b) Vogel A, Textbook of Practical Organic Chemislrl'. Vo\. 4 1971,3048. (Lol,lgman, New York), 1978, p 1202.

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