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CHEM1102 2014-J-8 June 2014 • Complete the following table. Make sure you give the name of the starting material where indicated. STARTING MATERIAL REAGENTS/ CONDITIONS O (CH3)2NH Cl hot 3 M NaOH STRUCTURAL FORMULA(S) OF MAJOR ORGANIC PRODUCT(S) Marks 4 CHEM1102 2014-J-9 June 2014 • Methylphenidate, also known as Ritalin, is a psychostimulant drug approved for the treatment of attention-deficit disorder. Identify all stereogenic (chiral) centres in methylphenidate by clearly marking each with an asterisk (*) on the structure below. methylphenidate Using one stereogenic centre you have identified, draw the (R)-configuration of that centre. How many stereoisomers are there of methylphenidate? Describe the relationships between these isomers. 4 isomers: there are 2 pairs of enantiomers: Each isomer has 1 enantiomer and 2 diastereoisomers Give the products formed when methylphenidate is hydrolysed with 4 M HCl. Marks 7 CHEM1102 2014-J-12 June 2014 • Show clearly the reagents you would use to carry out the following chemical conversions. More than one step is required in each case. Give the structure of any intermediate compounds formed. Marks 3 CHEM1102 2014-N-8 November 2014 Marks • Complete the following table. STARTING MATERIAL 1 REAGENTS/CONDITIONS THE MAJOR ORGANIC PRODUCT(S) O SOCl2 Cl CHEM1102 2014-N-9 November 2014 • Draw the structure of the organic product(s) formed when each of the following compounds is treated with 4 M sodium hydroxide. The first reaction requires heating. Compound Organic products O H 2N O N O OH O 3 CHEM1102 2013-J-9 June 2013 Marks • Complete the following table. STARTING MATERIAL 3 REAGENTS/ CONDITIONS SOCl2 CH3NH2 CONSTITUTIONAL FORMULA(S) OF MAJOR ORGANIC PRODUCT(S) CHEM1102 2013-J-14 June 2013 • Below is the reaction between an acid chloride and water to give a carboxylic acid. Provide curly arrows for this mechanism and draw the structures of the two intermediates on the pathway. Indicate the hybridisation of the two oxygen atoms in the starting materials. acid chloride: sp2 water: sp3 THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY. Marks 6 CHEM1102 2013-N-8 November 2013 Marks • Complete the following table. STARTING MATERIAL 1 REAGENTS/ CONDITIONS SOCl2 CONSTITUTIONAL FORMULA(S) OF MAJOR ORGANIC PRODUCT(S) CHEM1102 2013-N-12 November 2013 • The polymer Nylon 66 can be made by mixing the following two reagents. Draw the structure of Nylon 66. Marks 2 CHEM1102 2013-N-12 November 2013 • Consider the three compounds shown below. Arrange these compounds in order of increasing acidity. Explain your reasoning. Ethanol is the weakest acid as its conjugate base is not resonance stabilised. Phenol is a stronger acid as its conjugate base is resonance stabilised – the negative charge can be delocalised into the aromatic ring as shown below. There is even greater resonance stabilisation for the acetate ion (the conjugate base of acetic acid), as the negative charge is delocalised onto the electronegative oxygen atoms (as opposed to the carbon atoms in the case of phenol). Marks 3 CHEM1102 2013-N-13 November 2013 • The incomplete mechanism for the reaction of acetyl chloride with hydroxide ions is shown below. The reaction occurs in three steps. In each step complete the mechanism by adding curly arrows to indicate the bond changes taking place. Marks 3 CHEM1102 2012-J-9 June 2012 • Indicate the hybridisation of the carbon and nitrogen atoms in the diamine P. Draw the product of the reaction when diacyl chloride Q reacts with water. Kevlar (used in bullet-proof vests) is a polyamide polymer which is made from diacyl chloride building block Q and diamine building block P. Draw the repeating polymer unit formed in the reaction of P with Q. THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY. Marks 4 CHEM1102 2012-J-10 June 2012 • Complete the following table. If there is no reaction, write “NR”. Show any relevant stereochemistry. STARTING MATERIAL REAGENTS/ CONDITIONS Cr2O72– / H+ H+ catalyst / heat (CH3)2NH / heat CONSTITUTIONAL FORMULA(S) OF MAJOR ORGANIC PRODUCT(S) Marks 7 CHEM1102 2012-J-12 June 2012 • Consider the following molecule (M) isolated from a natural source. H N H2N COOH O (M) NH2 Give the products when molecule (M) is hydrolysed by heating it with 6 M HCl. Make sure you show the products in their correct ionisation states. Marks 6 CHEM1102 2012-J-13 June 2012 • Compound T is a precursor in the synthesis of the asthma drug salbutamol. Give the molecular formula of compound T. C11H12O4 Give the structure(s) of all organic products formed when compound T is heated with 4 M NaOH. THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY. Marks 3 CHEM1102 2012-N-10 November 2012 Marks • Complete the following table. STARTING MATERIAL 1 REAGENTS/ CONDITIONS SOCl2 CONSTITUTIONAL FORMULA(S) OF MAJOR ORGANIC PRODUCT(S) CHEM1102 2012-N-11 November 2012 • Draw the structure of the organic product(s) formed when each of the following compounds is treated with 4 M sodium hydroxide. The first two reactions proceed at room temperature; the last one requires heating. Compound Organic Product(s) THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY. Marks 4 CHEM1102 2010-J-11 June 2010 • Give the constitutional formula(s) of the major organic product(s) formed in each of the following reactions. Br COOCH3 1. LiAlH4 2. H / H2O 10 M HCl OH O 4 M NaOH O heat O N Me 6 M HCl heat H O O excess CH 3NH 2 Marks 7 CHEM1102 2010-N-9 November 2010 Marks • Complete the following table. STARTING MATERIAL 2 REAGENTS/ CONDITIONS O CONSTITUTIONAL FORMULA(S) OF MAJOR ORGANIC PRODUCT(S) O SOCl2 Cl OH O O H / H2O / heat CHEM1102 2010-N-10 November 2010 • The following is a nucleophilic addition-elimination reaction between ammonia and an acid anhydride. Provide curly arrows needed for the mechanism, and draw the structures of the two intermediates on this pathway. Marks 5 CHEM1102 2009-J-8 June 2009 • Complete the following table. Make sure you indicate any relevant stereochemistry. STARTING MATERIAL OH REAGENTS/ CONDITIONS CONSTITUTIONAL FORMULA(S) OF MAJOR ORGANIC PRODUCT(S) O 1. dilute NaOH 2. CH3Br O OH Br Cr2O72 / H OH 1. Mg / dry ether 2. H2O OH O COOH 1. NaBH4 2. H+ / H2O COOH The final product may react further: which might undergo intramolecular esterif ication to give the cyclic es ter OH COO H O O Marks 4 CHEM1102 2009-J-9 June 2009 • Give the constitutional formula(s) of the organic product(s) formed when each of the following compounds is treated with 4 M sodium hydroxide. The first three reactions proceed at room temperature; the last two require heating. COMPOUND ORGANIC PRODUCT(S) CH3CH2COOH CH3CH2CO2 H CH3 CH3 N Br CH3 H3C H 3C CH 3 H3C O H3C Cl O H 3C C O CH C CH C H3C CH3 N O Na O O H3C O C O Na + Na O O N O Na + H N Marks 7 CHEM1102 2009-J-9 June 2009 CHEM1102 2009-N-9 November 2009 Marks • Consider the following reaction sequence. 6 O OH K Reagent A Reagent B L M + O + O HCl N Compound K below can be converted into two different intermediates, L and M, which can react together to give compound N and the inorganic byproduct HCl. Give the reagents A and B and draw the structure of the intermediates L and M. A B SOCl2 1. LiAlH4 / dry ether L M O Cl HO 2. H+ / H2O CHEM1102 2009-N-10 November 2009 • Give the constitutional formula(s) of the organic products formed in each of the following reactions H NH2 N + OCH3 CH 3OH O O Br CN NaCN O 4 M NaOH O heat O + O OH Marks 3 CHEM1102 2008-J-8 June 2008 • Complete the following table. Make sure you indicate any relevant stereochemistry. STARTING MATERIAL REAGENTS/ CONDITIONS CONSTITUTIONAL FORMULA(S) OF MAJOR ORGANIC PRODUCT(S) CH3CH2COOCH2CH3 1. SOCl2 CH3CH2COOH O 2. CH3CH2OH O O O CH3CH2CH2CH2CH2OH CH3 C CH3 O O C C OCH2CH2CH2CH2CH3 O CH3 + CH3 C OH O O CH3 C H2O Cl O 1. LiAlH4 / dry ether H 2. H / H2O C CH3 C OH OH CH2 Marks 4 CHEM1102 2008-J-10 June 2008 • The structure of methyl 4-aminobenzoate, (E), is given below. O (E) O b H2N a Give the molecular formula of compound (E). C8H9NO2 Name the functional groups in molecule (E) indicated by the boxes “a” and “b”. a: amine b: ester Give the structure(s) of all organic products formed when compound (E) is treated with the following reagents. If no reaction occurs, write “NO REACTION”. cold HCl (1 M) No hydrolysis of the ester under these conditions. The amine group will be protonated by the strong acid. O O H3N hot NaOH (4 M) Treatment with base will lead to hydrolysis of the ester. In the basic solution, the carboxylic acid will be deprotonated and the amine will not be protonated. O O + CH3OH H2N hot HCl (4 M) Hydrolysis of ester. In acidic conditions, the carboxylic acid will not be deprotonated and the amine group will be protonated. O OH + CH3OH H3N Marks 5 CHEM1102 2008-N-10 November 2008 • The structure of the antihistamine, ZyrtecTM, is given below. What is the name of the functional group in Box A? Amine (tertiary) What is the name of the functional group in Box B? Ether What is the name of the functional group in Box C? Carboxylic acid By drawing an arrow on the structure above, clearly indicate the stereocentre in the structure of Zyrtec. Draw the product of the reaction when Zyrtec is treated with LiAlH4 followed by dilute acid. LiAlH4 will reduce the carboxylic acid all the way to an alcohol. Marks 5 CHEM1102 2007-J-7 June 2007 • Draw the structure of the major organic product formed in the following reactions. HO O CH3 1. CH3MgBr 2. H / H2O O O OH CH3CH2OH / H O O 1. NaBH4 2. H / H2O OH Marks 5 CHEM1102 2007-J-8 June 2007 Marks • Suggest reagents you could use to achieve the following transformations. O 4 O A OCH3 O Na B O Br C intermediate compound D OH A: NaOH / H2O / heat B: H2 / Pd catalyst C: Mg / dry ether D: 1.CO2 2. H / H2O CHEM1102 • 2007-J-10 June 2007 Marks The amino acids serine and valine are shown below. 7 OH H H2N 4 CO2H serine H H 2N 1 3 CO2H 2 valine List the substituents attached to the stereogenic centre of valine in order of decreasing priority. highest priority -NH2 lowest priority -COOH -CH(CH3)2 Assign the absolute configuration of the stereoisomer of valine shown above. -H (S) (anticlockwise) Draw a dipeptide formed by the condensation of serine with valine. H2N CH CO NH CH COOH CH2OH What are the two key elements of protein secondary structure? The secondary structure describes the orientation of segments of the peptide chain and is defined by the H-bonding between amino acid residues. The most common secondary structures are: - α-helices, right handed coils stabilized by H-bonds between amide NH and C=O groups four residues apart and - β-pleated sheets, extended structures stabilized by H-bonds between amide N-H and C=O groups on different chains CHEM1102 2007-N-9 November 2007 • The structure of salbutamol, a drug used to treat bronchospasms, is given below. OH H N HO HO Give the molecular formula of salbutamol. C13H21O3N Calculate the m/z value for the major peak you would expect to see for the molecular ion in the high resolution mass spectrum. [Atomic masses: 1H = 1.0078; 12C = 12.0000; 16O = 15.9949; 14N = 14.0031] The molar mass of C13H21O3N is 13 × 12.0000 (C) + 21 × 1.0078 (H) + 3 × 15.9949 (O) + 1 × 14.0031 (N) Answer: 239.1516 Give the structure(s) of the major organic products formed when salbutamol is treated with the following reagents. OH cold HCl (1 M) H N HO H HO OH NaOH (1 M) H N HO O O Cr2O72 / H O H N HO HO Marks 5 CHEM1102 2007-N-10 November 2007 Marks • Complete the following table. Starting material 2 Reagents / Conditions O C Major organic product(s) O OH H SOCl2 C Cl 1. NaBH4 O 2. H / H2O OH THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY. CHEM1102 2007-N-11 November 2007 • Consider the reaction sequence below. 2 O O OH O A Cl + B H Draw the structures of products A and B. A B O O OH O Cl • Draw the structure of the product, C, from the following reaction. C O O excess H2 O OCH3 Pd/C catalyst O OCH3 Product C undergoes hydrolysis when heated with 4 M NaOH. Give the structures of the products (in their correct ionic states) formed in this reaction. O HO O OCH3 3 CHEM1102 2007-N-12 November 2007 • The incomplete proposed mechanism for the reaction of acetyl chloride with ammonia is shown below. Complete the mechanism by adding curly arrows to illustrate the bonding changes that take place. O O Cl H Cl N H NH3 O O Cl + H NH2 Cl N + H H H THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY. Marks 5 CHEM1102 2006-J-7 June 2006 • Draw the structure of the major organic product formed in the following reactions. O O SOCl2 OH OH Cl OH O 1. LiAlH 4 H 2. H / H 2O OH Marks 5 CHEM1102 • 2006-J-10 June 2006 Marks The amino acid serine is shown below: HO (c) 6 H H2N (a) COOH (b) List the substituents attached to the stereogenic centre in order of decreasing priority. highest priority lowest priority NH2 COOH CH2OH H S Assign the absolute configuration of the stereoisomer shown above. Draw the dipeptide formed by the condensation of two serine residues. NH2 CH CO NH CH CH2OH COOH CH2OH Explain briefly what is meant by the primary structure of a protein. The primary sequence is the sequence in which the amino acids occur. For example, ala-ser-tyr: • Draw the repeating unit of the polymer formed in the following reaction. O Cl Cl O + NH2 H2N O H N N O H n 2 CHEM1102 2006-N-7 November 2006 Marks • The structure of lignocaine, a local anaesthetic, is given below. 7 H N N O b a Give the molecular formula of lignocaine. C14H22ON2 Name the functional groups in lignocaine indicated by boxes “a” and “b”. a: amide b: tertiary amine Give the structure(s) of all organic products formed when lignocaine is treated with the following reagents. If no reaction occurs, write “NO REACTION”. H cold HCl (1 M) N N H O O hot NaOH (4 M) NH2 N O hot HCl (4 M) HO NH3 N O H CHEM1102 2006-N-8 November 2006 • Draw the constitutional formula of the major organic product formed in each of the following reactions. O O OH Cl SOCl2 O OH CH3COOH H / heat OH Cr2O7 COOH 2 O O /H 1. LiAlH 4 2. H / H 2O OH Marks 6