Module Details

The information contained in this module specification was correct at the time of publication but may be subject to change, either during the session because of unforeseen circumstances, or following review of the module at the end of the session. Queries about the module should be directed to the member of staff with responsibility for the module.
Title ORGANIC CHEMISTRY III (BSC.)
Code CHEM331
Coordinator Dr RP Bonar-Law
Chemistry
R.P.Bonar-Law@liverpool.ac.uk
Year CATS Level Semester CATS Value
Session 2015-16 Level 6 FHEQ First Semester 15

Pre-requisites before taking this module (or general academic requirements):

Completion of year 2 of either an MChem or a BSc (Hons) Chemistry programme 

Aims

The aim of the course is to consolidate and extend second year knowledge of synthetic and physical organic chemistry, and introduce some aspects of biological chemistry.


Learning Outcomes

By the end of the module, students should:

  • Demonstrate a good understanding of modern synthetic reactions and their mechanisms.
  • Demonstrate familiarity with some of the more important aspects of biological chemistry

Teaching and Learning Strategies

Lecture -

Tutorial -


Syllabus

1
Organic synthesis and reactions (14)
 
 
 
 
Pericyclic reactions 1: cycloadditions (3 lectures)
  • The rules that govern cycloadditions
  • Photochemical reactions: reactions that need light
  • Making six-membered rings by the Diels–Alder reaction
  • Making four-membered rings by [2 + 2] cycloaddition
  • Making five-membered rings by 1,3- dipolar cycloaddition
  • Using cycloaddition to functionalize double bonds stereospecifically
  • Using ozone to break C=C double bonds
Pericyclic reactions 2: Sigmatropic and electrocyclic reactions (2 lectures)
  • Stereochemistry from chair-like transition states
  • Making γ,δ-unsaturated carbonyl compounds
  • What determines whether these pericyclic reactions go ‘forwards’ or ‘backwards’
  • Fischer Indole synthesis
  • Why substituted cyclopentadienes are unstable
  • What ‘con’- and ‘dis’-rotatory mean
  • Reactions that open small rings and close larger rings
Rearrangements and Fragmentations (3 lectures)
  • Participation means acceleration and retention of stereochemistry and may mean rearrangement
  • Participating groups can have lone pairs or π-electrons
  • Carbocations often rearrange by alkyl migration
  • Ring expansion by rearrangement
  • Using rearrangements in synthesis
  • Electron donation and electron withdrawal combine to create molecules that fragment
  • Anti-periplanar conformation is essential
  • Small rings are easy to fragment, medium and large rings can be made in this way
  • Double bond geometry can be controlled
  • Using fragmentations in synthesis
Radical reactions (3 lectures)
  • Radical reactions follow different rules to those of ionic reactions
  • Bond strength is very important
  • Radicals can be formed with Br, Cl, Sn, and Hg
  • Efficient radical reactions are chain reactions
  • There are electrophilic and nucleophilic radicals
  • Radicals favour conjugate addition
  • Cyclization is easy with radical reactions
  • Dissolving metal reductions with metal-ammonia systems applied to aromatic systems (Birch reduction) and enones and their synthetic applications. Dissolving metal reductions applied to carbonyl groups - Pinacol coupling and acyloin condensation.
Synthesis of alkenes -- controlling double bond geometry (2 lectures)            
  • Stereospecific eliminations reactions.                            
  • Wittig, Peterson and Julia reactions                            
  • Reduction of alkynes                                      
Physical organic chemistry (8 lectures)
  • Revision of basic mechanisms            
o SN2, SN1                             
o E1, E2, E1cb                            
o Electrophilic addition and substitution reactions                            
o Nucleophilic substitution at carbonyls                    
  • Equilibrium and rates            
o Revision of basic thermodynamics: DGo = -RTln(K) = DHo - TDSo                           
 
o Acid-base equilibria: pKa of common acids                             
o Reaction coordinate, transition state, microscopic reversibility                            
o Connection between equilibrium and rate constants K = k1/k-1                

 
 
  • Rates, Equilibria and Free Energy Diagrams            
o Hammond''s postulate                             
o Thermodynamic vs. kinetic control                             
o Curtin-Hammett principle                             

 
 
  • Ki
    netics            
o Revision of elementary kinetics                             
o Multistep reactions, bottlenecks, rate determining step and steady state approximation, connection with free energy diagrams                              
o Primary deuterium kinetic isotope effect
 
 
 
 
                             
Introduction to bioorganic chemistry -- essay and web based project
Topics:
  • Carbohydrate chemistry            
o Nomenclature and conformation of monosaccharides and selected oligosaccharides.      
      
o The hemiacetal, glycosidic bond and naturally occurring glycosides.            
o Glycoside synthesis.            
  • Nucleic acid chemistry            
o Structure of purine and pyrimidine bases and nucleosides.            
o Base pairing and introduction to nucleic acid structure.            
  • Amino acid and protein chemistry            
o Structures of amino acids.            
o The peptide bond.            
o Introduction to 1o, 2o and 3o - structure of protein
s.            
o Relationship of protein and DNA sequence.            

Recommended Texts

Reading lists are managed at readinglists.liverpool.ac.uk. Click here to access the reading lists for this module.
Explanation of Reading List:

Teaching Schedule

  Lectures Seminars Tutorials Lab Practicals Fieldwork Placement Other TOTAL
Study Hours 22

  3

      25
Timetable (if known)              
Private Study 125
TOTAL HOURS 150

Assessment

EXAM Duration Timing
(Semester)
% of
final
mark
Resit/resubmission
opportunity
Penalty for late
submission
Notes
Written Exam  2 hours  1st Semester  65  August resit opportunity for PGT students only where applicable. see notes    Assessment 2 Notes (applying to all assessments) Essay and web based project Essay during first half of semester (17.5%), web-based project in second half (17.5%). This work is not marked anonymously Examination Year 3 (and Year 4) students resit at the next normal opportunity.  
CONTINUOUS Duration Timing
(Semester)
% of
final
mark
Resit/resubmission
opportunity
Penalty for late
submission
Notes
Coursework    1st semester  35  No  Standard University Policy applies - see Department/School handbook for details.  Assessment 1