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 FURTHER ORGANIC CHEMISTRY
Code CHEM333
Coordinator Dr RP Bonar-Law
Chemistry
R.P.Bonar-Law@liverpool.ac.uk
Year CATS Level Semester CATS Value
Session 2018-19 Level 6 FHEQ First Semester 15

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

 

Aims

The aim of the course is to extend second year knowledge of synthetic and physical organic chemistry.


Learning Outcomes

(LO1) By the end of the module, students should: Have a good understanding of modern synthetic reactions and their mechanisms. Be able to deduce mechanisms on the basis of kinetic and other evidence.


Teaching and Learning Strategies

Teaching Method 1 - Lecture
Description:
Attendance Recorded: Yes

Teaching Method 2 - Tutorial
Description:
Attendance Recorded: Yes


Syllabus

 

Organic synthesis and reactions (20 lectures)   Pericyclic reactions 1: cycloadditions 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 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 Participati on 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 Radical reactions follow different rules to those of ionic reactionsBond 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 reactionsDissolving metal reductions with metal-ammonia systems applied to aromatic systems (Birch reduction) and enon es and their synthetic applications. Dissolving metal reductions applied to carbonyl groups - Pinacol coupling and acyloin condensation.   Phosphorus Wittig, Wittig-Horner and Wadsworth-Emmons reactions and their use in synthesis. Aza-Wittig reaction.Mitsunobu reaction, mechanism and applications .   Sulfur Introduction to organosulfur compounds (oxidation states, names etc.). Synthesis and chemistry of sulfoxides, allylic sulfoxide-sulfenic ester rearrangement. Pummerer reaction, syn elimination of sulfoxides.   Sulfones   Julia reaction, Ramberg Backlund reaction and extrusion of SO2 from sulfolenes. Chemistry of sulfur ylids, Corey/Trost reagents.   Selenium Comparison of sulfur and selenium compounds. Reactions of selenoxides, syn elimination and [2,3] sigmatropic rearrangements. Oxidation reactions of selenium dioxide. Selenium mediated cyclisation reactions (PhSeCl etc.).     Physical organic chemistry (11 lectures)   Equilibria, transition states and rates Free energy diagrams, transition states, connection between equilibrium and rate constants K = k1/k-1, Hammond’s postulate, thermodynamic vs kinetic control, Curtin-Hammett.         Kinetics Revision of elementary kinetics, steady state for multistep reactions, primary deuterium kinetic isotope effect.           S N 2, S N 1 Mostly revision of year 2 material   Elimination reactions Revision of E1, E2, E1cb, kinetics, mechanistic continuum        Addition reactions Revision of HX, X 2 additions with kinetics, some synthetic applications   Nucleophilic substitution at carbonyls Tetrahedral intermediates and mechanisms for ester hydrolysis.   The Hammett equation     Substituent constants, reaction constants, correlation of rates and equilibria, multistep reactions, physical basis of LFER.


Recommended Texts

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

Teaching Schedule

  Lectures Seminars Tutorials Lab Practicals Fieldwork Placement Other TOTAL
Study Hours 37

  5

      42
Timetable (if known)              
Private Study 108
TOTAL HOURS 150

Assessment

EXAM Duration Timing
(Semester)
% of
final
mark
Resit/resubmission
opportunity
Penalty for late
submission
Notes
Assessment 2 There is a resit opportunity. Standard UoL penalty applies for late submission. This is an anonymous assessment. Assessment Schedule (When) :1st Semester  3 hours    80       
CONTINUOUS Duration Timing
(Semester)
% of
final
mark
Resit/resubmission
opportunity
Penalty for late
submission
Notes
Assessment 1 Standard UoL penalty applies for late submission. This is not an anonymous assessment. Assessment Schedule (When) :1st Semester  5x1 hour problem set    20