Chemistry of Nitrogen-containing Organic Compounds FSF = Full Structural Formula

Key Areas Functional group – name and structure Characteristic chemical reactions - type - reactants - products - conditions - mechanism

Nitrogen-containing Functional Groups NITRILES NITRILES AMINES AMINES AMIDES AMIDES AMINO ACIDS AMINO ACIDS POLYAMIDES POLYAMIDES

NITRILES Not to be confused with cyanides (CN - ) First member is ethanenitrile. Draw the full structural formula. Name the fourth member of the family. C N very polar Will the C-atom be a nucleophile or electrophile? CNR

Producing nitriles Halagenoalkanes - heating under reflux with NaCN or KCN in ethanol - draw the FSF for 1-bromobutane and then for the nitrile produced on reaction with KCN - what type of reaction is this? - what is significant about the length of the carbon chain?

Reaction mechanism ++ -- CH 3 H I C H CN - CH 3 H CN C H I - propanenitrile

Characteristic Reactions Hydrolysis - under acid or alkaline conditions - occurs in two steps: Carboxylic acids CH 3 C O NH2NH2 CN H3CH3C + H 2 O 1 HYDRATION AMIDE CH 3 C O NH H 2 O CH 3 C O OH CARBOXYLIC ACID + NH 4 + NUCLEOPHILIC SUBSTITUTION

Reduction - Lithium tetrahydridoaluminate(III) - in dry ether Characteristic Reactions Amines CH 3 -CH 2 -NH 2 CN H3CH3C + 4[H] REDUCTION AMINE Draw the FSF for the compound produced when butanenitrile is reduced.

AMINES Relatives of NH 3, where H’s have been replaced by a hydrocarbon chain Naming: CH 3 -NH 2 NH 2 AMINO GROUP METHYLAMINE METHYLAMINE or….. AMINOMETHANE

AMINES Draw the full structural formula for 2- propylamine and give its alternative name. What types of INTERMOLECULAR FORCES exist in amines? NH 2 AMINO GROUP

AMINE STRUCTURE Amines can be classed as primary, secondary or tertiary NH 2 AMINO GROUP PRIMARY TERTIARY SECONDARY

Producing amines 1 Halogenoalkanes - heat with ammonia in ethanol Overall, what type of reaction is this? 1 2

Producing amines 2 Nitriles (What is a nitrile?) -C≡N - reduction - using LiAlH 4 (in dry ether + water) Draw the simplified strucural formula for the amine produced by reducing butanenitrile.

Reactions of amines As bases N H H H Primary amines, although weak bases, are stronger than ammonia Explained by the inductive effect

Inductive Effect N H CH 3 H Alkyl groups are electron donating (INDUCTIVE EFFECT) H+H+ More Alkyl groups = GREATER INDUCTIVE EFFECT  MORE BASIC

Reactions of amines 2 As nucleophiles - with acid chlorides (acyl chlorides) 1.Find out what an acyl chloride is and draw the general structure. 2.Draw a reaction mechanism for an acyl chloride with 3 carbon atoms reacting with ethylamine. 3.What is this type of reaction called? 4.What type of organic compound is the product? N H H H

AMIDES Are white crystalline solids at room temperature (expect methanamide) Are important in polymer chemistry How can amides be made in the lab? R-C O NH 2

Reactions of amides HYDROLYSIS Using acid or alkali This is the same as the second step as when nitriles are hydrolysed Using the notation as above, use FSF to draw the hydrolysis carried out under alkaline conditions CH 3 C O NH 2 + H 3 O + CH 3 C O OH CARBOXYLIC ACID + NH 4 + NUCLEOPHILIC SUBSTITUTION

Reactions of amides 2 DEHYDRATION Heating an amide with phosphorus(V) oxide dehydrates the compund. Using FSF, construct an equation for the dehydration of an amide with 4 carbon atoms. Name the amide. What type of organic compound is produced?

AMINO ACIDS Are the building blocks of proteins About 20 in total Draw the FSF for a chiral amino acid Draw the FSF of an amino acid when it is in: Water Acid Alkali R C C H O OHOH N H H Zwitterion

Reactions of amino acids Amino acids join together to form peptides This is a condensation reaction An AMIDE group amide N H RR 1 C O Draw the FSF of a peptide consisting of alanine, cysteine and serine

POLYAMIDES Formed from a diamine and a diacid Nylon is a polyamide Kevlar is an aramid Used to make bullet-proof vests C O HO R C O OH N H H R N H H