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A-LevelChemistryOrganic synthesis9701/42 · Feb/Mar 2020 · Q611 Marks

Valinol can be synthesised by the following reactions. Reaction 1 uses valine as the starting material. [Figure 6.1]

  1. (a)(i)Write an equation for reaction 1, using [H] to represent the reducing agent.[1]
  2. (a)(ii)Suggest a suitable reagent for reaction 1.[1]
  3. (a)(iii)Name the mechanism for reaction 2.[1]
  4. (b)Valine and glycine, H₂NCH₂COOH, form the tripeptide Gly-Val-Gly. Draw the structure of this tripeptide. Show the peptide bonds fully displayed.[2]
  5. (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]
  6. (c)(ii)Valine is an amino acid. Draw the zwitterion of valine.[1]
  7. (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]
  8. (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]
  9. (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]

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Mark scheme

Marking points from the official mark scheme (Feb/Mar 2020). The mark or mark type is shown in brackets.

  1. [1] (CH3)2CHCHNH2COOH + 4[H] → (CH3)2CHCHNH2CH2OH + H2O OR C5H11NO2 + 4[H] → C5H13NO + H2O
  2. [1] lithium aluminium hydride / LiAlH4 (in dry ether)
  3. [1] nucleophilic substitution
  4. [2] M1 one peptide link fully displayed (but not contradicted by the other peptide link)
  5. M2 rest of structure correct
  6. [2] M1 optical isomerism
  7. M2 (two structures of valine enantiomers)
  8. [1] (structure of valine zwitterion)
  9. [1] Kstab = [Ni(H2O)2Val2] / [Ni(H2O)62+][Val-]2
  10. [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-)
  11. [1] bidentate

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About this question

Topic
Organic synthesis, A-Level Chemistry (syllabus 9701). Structured question, 11 marks.
Source
A-Level Chemistry, Feb/Mar 2020 Paper 4 Variant 2, question 6.

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