PETER SENTONGO (B119092) Molecular Basis of Life CMA009 Experiment 3.

3 THE BECKMANN REARRANGEMENT The synthesis of a Carprolactam This experiment will the demonstrate the preparation of an oxime from ketone and the acid-catalysed rearrangement of the oxime to produce an amide (the Beckmann Rearrangement.) The product caprolactam is used in the production of a type of nylon. The experiment reaction is illustrated below:
O O H2NOH NOH H2SO4

NH

Cyclohexanone Chemical Formula: C6H10O Molecular Weight: 98.14

Cyclohexanone oxime Chemical Formula: C6H11NO Molecular Weight: 113.16

Caprolactam azepan-2-one Chemical Formula: C6H11NO Molecular Weight: 113.16

Procedure Part A The preparation o f cyclohexanone oxime Dissolved 7g of hydroxylamine hydrochloride and 12g of sodium acetate in 30ml water in a 250ml round-bottomed flask. Warmed the solution using a steam bath to about 40C and added 7g of Cyclohexanone. Swirl the flask rapidly without stoppering it for about 10min, warmed the solution occasionally. Allowed the flask to cool down and collected the crystals of oxime by filtration using a Buchner flask. Then washed the crystals with a small amount of cold water and finally recrystallized the crude oxime from the petroleum ether and dried in air. Part A results Melting point: 87-90 (literature melting point = 90) 1 Mass of Product: 7.598g Percentage Yield: 95% No. Of moles of C6H10O = 7/(12.011 x 6) + (1.0079 x 10) + (15.999), 7/98.756 = 0.07088 moles

No. Of Moles of C6H11ON = mass of product (7.598/RMM), 7.598 / ((12.011 x 6) + (1.0079 x 11) + (15.999) + (14.007)) 7.598 / 113.1589 = 0.06715 % Yield = (0.06715 / 0.07088) x 100 = 94.73 % Yield = 95% IR Spectra: The IR spectrum of was cyclohexanone oxime obtained, the absorption band was observed at 2843,2889,2925 and 2977 cm in the IR spectrum represent the presence of the ketone, C=O, NO, O-H and the stretching of the oxime ring. Part B: The preparation of caprolactam the Beckmann Rearrangement. Placed 8.5ml of concentrated sulphuric acid in a dry 500ml conical flask and slowly added 4g of the pure oxime whilst swirling the flask. Heated the reaction mixture for 10min using a steam bath. Allowed the exothermic reaction to subside and cooled the flask in an ice bath. Poured a cold mixture onto a 130g ice and slowly added 1M of sodium hydroxide solution until the mixture was slightly alkaline, kept the temperature below 10C during the addition. Transferred the mixture into a 500ml separatory funnel and extracted with 3 x 75ml portions of ethyl acetate. Combined the organic extracts and dried them over anhydrous magnesium sulphate and evaporated to dryness on a rotary evaporator to yield the crude oily product. Then added hot light petroleum (heated on a steam bath to the crude product and swirl the flask to dissolve the residue and allowed the flask to cool and crystallised out the caprolactam, which was then isolated by filtration using a Buchner flask. Part B results: Product Yield: 2.362g Melting point: 68-69 (literature melting point = 69) 1 Percentage Yield: 59% No. Of Moles of C6H11ON 4 / ((12.011 x 6) + (1.0079 x 11) + (15.999) + (14.007)) 4 / 113.1589 = 0.03535 moles No. Of Moles of C6H11ON based on product mass of Caprolactum 2.362 / 113.1589 = 0.02087 moles % Yield = (0.02087 / 0.03535) x 100 = 59.05 % Yield = 59%

IR Spectra: The IR spectrum of caprolactum was obtained and was similar to that of cyclohexanone oxime, the absorption band were observed at 2843,2889,2925 and 2977 cm in the IR spectrum represent the presence of the ketone group, C=O, NO, OH and the stretching of the oxime ring. However, the caprolactum peaks where smaller than that of cyclohexanone oxime. Both spectra have similarities in the position of their peaks in comparison to the student cyclohexanone spectra provided by the technicians which implies that experiment was done properly thus obtained the intended products respectively. Discussion of the results The products obtained in this experiment were pure because their melting points obtained, agree within the literature melting points of the both Oxime and Caprolactum. The IR spectra also illustrate the presence of the different functional groups at various peaks resent in the products and the spectra have a huge similarities with the spectra provided from the technicians. Good % yields where also obtained. Problem The full reaction mechanism of oxime formation.
Proton lost
O N OH2 NH

NH2OH

H2O

H O N N HO H N

NH

Reference: 1. http://www.chemexper.com/chemicals/supplier/cas/90-90-4.html