CORK INSTITUTE OF TECHNOLOGY INSTITIÚID TEICNEOLAÍOCHTA CHORCAÍ
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1 CORK INSTITUTE OF TECHNOLOGY INSTITIÚID TEICNEOLAÍOCHTA CHORCAÍ Module Title: Topics in Organic Chemistry Module Code: CHEO 7003 School : Science Programme Title: Bachelor of Science in Analytical & Pharmaceutical Chemistry Stage 3 BSc. in Analytical Chemistry with Quality Assurance Stage 3 Programme Code: SCHEM_7_Y3 SCQUA_8_Y3 External Examiner(s): Internal Examiner(s): Dr Claire Lennon Dr W O Doherty Instructions: Answer four question in total. Each question carries equal marks Duration: 2 hours Sitting: Christmas 2013 Date: Requirements for this exam: Chemical Shift Tables Note to Candidates: Please check the Programme Title and the Module Title to ensure that you have received the correct examination paper. If in doubt please contact an Invigilator.
2 Q1. (a) Explain what is meant by keto-enol tautomerisation. Give an example of such tautomerism. (b) (i) List the component reactions of the Robinson annulation reaction. [4 marks] (ii) Give the product, A, of the Robinson annulation reaction for the following reagents [8 marks] (iii) The Robinson annulation is often not carried out as a single pot reaction in particular when using the above conditions. One of the products of the component reactions is isolated first. At what stage is this isolation carried out? Why is this done, what complications/side reactions can occur? [8 marks] Q2. (a) Tartaric acid has a structure as given in the following diagram. It has two chiral centres. (i) (ii) How many possible stereoisomers can be drawn for any molecule with two chiral centres? Highlight the chiral centres in tartaric acid with an asterisk* (redraw in your answer book). [4 marks] Draw the 2S,3R and 2R,3S stereoisomers of tartaric acid. In your answer, explain your use of the Cahn-Ingold-Prelog sequence rules. [6 marks]
3 (b) (iii) What is the relationship between the 2S,3R and 2R,3S stereoisomers of tartaric acid. [3 marks] The following product is a result of a mixed aldol condensation reaction. (i) What are the two carbonyl starting materials? [4 marks] (ii) Identify which is the nucleophile and which is the electrophile. [2 marks] (iii) What are the other possible structures that could be formed from the two carbonyl starting materials that you have indicated in part (i). Why can these other products be formed? [6 marks] Q3. (a) Explain what is meant by the term effective magnetic field strength. [4 marks] (b) (i) Explain the origin of splitting in an NMR spectrum. [3 marks] (ii) Construct the splitting pattern you would expect to see for the Ha protons in the following molecule. Assume 3 J ac ~ 3 J ab. [8 marks] (c) Deduce the structure of the compound with molecular formula C 11 H 22 O 2 from the following IR and 1 H NMR data:
4 IR: 1740cm -1 strong 1250cm -1 strong NMR: (ppm) multiplicity peak area Coupling constant(s) (Hz) 0.86 s d t m / t d [10 marks] Q4. (a) Write the mechanism for the solid-state Merrifield peptide synthesis. In answer clearly identify the role of blocking and activating groups. [10 marks] (b) Explain how Edman s Reagent is used to determine the amino acid sequence in a peptide chain. Show a general reaction mechanism detailing the cleavage of the peptide bond. [9 marks] (c) What is the isoelectric point and how is it determined for an amino acid? [6 marks]
5 Q5 (a) The following pyridine can be synthesized using the Hantzsch synthesis method. (b) (i) Detail the starting materials, and reagents required. (ii) This is a multi-step process, which involves an ester enamine as a key intermediate. Draw the mechanism for reaction that produces this ester enamine, using the reagents above. [10 marks] (iii) What is the driving force for the production of the pyridine from the dihydropyridine derivative? To prevent side reactions in a mixed aldol reaction, it is necessary for one of the reagents to be electrophilic only. Give an example of such a reagent and explain why it can only act as an electrophile. Q6 (a) (i) Detail the reagents used in the haloform test and the characteristic product that indicates a positive test result. [3 marks] (ii) Give a structure of an alcohol with the formula C 5 H 11 OH that would give a positive haloform result. (b) Discuss the difference between kinetic and thermodynamic enolate anions and their formation. Give examples of the relevant structures of these enolates anions and reagents that would be used to produce the relevant anions. [9 marks] (c) What is meant by optically active molecules? [3 marks] (d) What is meant by the terms absolute configuration and relative configuration of a molecule
6
A Grignard reagent formed would deprotonate H of the ethyl alcohol OH.
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