CHEM1042 Fundamentals of Organic Chemistry II for non-chemists

Module Overview

Aims and Objectives

Learning Outcomes

Having successfully completed this module you will be able to:

Understand the influence of bond polarisation on a molecule’s structure and reactivity
Recognise many functional groups and their reactivity
Recognise many fundamental bond forming reactions and how to apply them in synthesis
Describe bonding models and appreciate how these impact on the properties of a simple molecule
Apply curly arrow nomenclature to depict the mechanistic course of a reaction
Appreciate when different reactions are likely to compete and ways to bias reactions towards a single outcome
Understand and apply the concept of protecting groups
Understand how spectroscopic techniques can be used to delineate a molecule’s structure

Syllabus

• Applications of nucleophilic substitution reactions: Synthetic value of reactions of alkyl halides and sulfonates with nucleophiles. Revision of key features of SN1 and SN2 reaction mechanisms (including allylic and benzylic systems). Formation of alcohols by hydrolysis of alkyl halides. Reactions of alcohols with strong acids e.g. reaction with HX to form alkyl halides and dehydration to give alkenes. Use of thionyl chloride and phosphorous pentabromide to form alkyl halides (including mechanisms). Use of nitrogen, sulfur and phophorus nucleophiles. • Organometallic reagents for C-C bond formation: the chemistry of Grignard reagents (reversal of polarisation at carbon). Formation by reaction with alkyl halides – reaction conditions. Grignards as bases (reactions with water, alcohols and alkynes). • The elimination reactions: Substitution vs elimination in alkyl halides. Dehydration of alcohols. Elimination mechanisms (E1, E2 and E1cb). Stereochemistry and regioselectivity in elimination reactions. • Electrophilic additions to alkenes: addition to alkenes of hydrogen halides, including regio- and stereochemistry for Markovnikov and anti-Markovnikov additions. Bromination of alkenes via a bromonium ion leading to the formation of trans-1,2-dibromides and bromohydrins. Epoxidation (peracids, and via bromohydrin), hydroboration (basic mechanism) and dihydroxylation (e.g. with OsO4, and via epoxide hydrolysis) of alkenes. • Nucleophilic addition to the carbonyl group: • Introduction - structure and bonding, polarisation, oxidation levels, leaving group ability and the influence of attached atoms on reactivity. Principle reactions with nucleophiles, electrophiles and bases and loci of reactivity. Addition of HCN, hydride, organometallic reagents • Nucleophilic substitution at the carbonyl group: Acetal and imine formation, the Wittig reaction (basic mechanism). • Nucleophilic substitution at the carbonyl group in carboxylic acid derivatives: Addition-elimination reactions, the tetrahedral intermediate. Mechanism of formation of esters from acids and alcohols – role of acid catalysis. Preparation using acid chlorides. Hydrolysis of esters (acid and base-catalysed – including simple mechanisms), Reactions with nucleophiles: (i) with simple Grignards; (ii) with amines; (iii) reduction by LiAlH4., Formation of amides from acid chlorides and esters. Hydrolysis (low reactivity). Nitriles: Formation from alkyl halides. Hydrolysis to carboxylic acids. Reactions with nucleophiles: (i) reduction by hydride reducing agents; (ii) reactions with simple Grignard reagents to give ketones. • An introduction to enolate chemistry: Including α-alkylation of aldehydes, ketones and acid derivatives

Learning and Teaching

Teaching and learning methods

Lectures, problem-solving seminars with group working and tutor support. Feedback is provided • In tutorials through assistance with the set work. • Through the marks achieved in the in online tests. • Through generic feedback following the examinations.

Type	Hours
Lecture	24
Revision	5
Preparation for scheduled sessions	24
Wider reading or practice	17
Tutorial	5
Total study time	75

Resources & Reading list

Andrew Burrows, John Holman, Andrew Parsons, Gwen Pilling, and Gareth Price (2009). Chemistry3: Introducing inorganic, organic, and physical chemistry.

M. Hesse, H. Meier, B. Zeeh (2008). Spectroscopic Methods in Organic Chemistry.

James Keeler and Peter Wothers (2008). Chemical Stucture and Reactivity.

D. Williams, I. Flemming (2008). Spectroscopic Methods in Organic Chemistry.

J Clayden, N Greeves and S Warren (2012). Organic Chemistry.

Assessment

Formative

Tutorial

Summative

Method	Percentage contribution
Assessed Tutorials	10%
Examination (2 hours)	90%

Referral

Method	Percentage contribution
Examination (2 hours)	100%

Repeat Information

Repeat type: Internal & External

Linked modules

Pre-requisites: CHEM1041 or CHEM1031