Valinol can be synthesised by the following reactions. Reaction 1 uses valine as the starting material. [Figure 6.1]
- (a)(i)Write an equation for reaction 1, using [H] to represent the reducing agent.[1]
- (a)(ii)Suggest a suitable reagent for reaction 1.[1]
- (a)(iii)Name the mechanism for reaction 2.[1]
- (b)Valine and glycine, H₂NCH₂COOH, form the tripeptide Gly-Val-Gly. Draw the structure of this tripeptide. Show the peptide bonds fully displayed.[2]
- (c)(i)Valine exists as two stereoisomers. Draw three-dimensional diagrams to show the two stereoisomers of valine. In your diagrams, the –CH(CH₃)₂ group can be represented by -R. State the type of stereoisomerism shown. type of stereoisomerism[2]
- (c)(ii)Valine is an amino acid. Draw the zwitterion of valine.[1]
- (c)(iii)Valinate, Val⁻, is the anion of valine. It takes part in a ligand substitution reaction with hexaaquanickel(II) ions. Complex Z is formed. [Ni(H₂O)₆]²⁺(aq) + 2Val⁻(aq) ⇌ [Ni(H₂O)₂(Val)₂](aq) + 4H₂O(l) Write an expression for Kstab for this equilibrium. Kstab =[1]
- (c)(iv)At room temperature, the numerical value of Kstab is 2.34 × 10⁵. Explain what this value indicates about the equilibrium and the stability of complex Z.[1]
- (c)(v)Z is an octahedral complex with formula [Ni(H₂O)₂(Val)₂]. Use this information to state the type of ligand that the valinate ion is acting as in this complex.[1]
This question uses a diagram from the original paper, which isn't shown here. Open the full paper from the past papers archive to see it.
Mark scheme
Marking points from the official mark scheme (Feb/Mar 2020). The mark or mark type is shown in brackets.
- [1] (CH3)2CHCHNH2COOH + 4[H] → (CH3)2CHCHNH2CH2OH + H2O OR C5H11NO2 + 4[H] → C5H13NO + H2O
- [1] lithium aluminium hydride / LiAlH4 (in dry ether)
- [1] nucleophilic substitution
- [2] M1 one peptide link fully displayed (but not contradicted by the other peptide link)
- M2 rest of structure correct
- [2] M1 optical isomerism
- M2 (two structures of valine enantiomers)
- [1] (structure of valine zwitterion)
- [1] Kstab = [Ni(H2O)2Val2] / [Ni(H2O)62+][Val-]2
- [1] equilibrium lies (well) to the right / towards the products AND (Z) is stable / more stable (than [Ni(H2O)6]2+ in the presence of Val-)
- [1] bidentate
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