Things to Know for the Final Exam Chapter 9 Chapter 14

Things to Know for the Final Exam
Chapter 9
Solving 1H NMR’s by examining chemical shift, integration, and splitting of the
Chapter 14
Aromaticity rules, 1) planar ring, 2) all atoms sp2 hybridized with a p orbital, 3)
Huckels rule (4n+2)
Aromatic heterocycles
Aromatic anions and cations
Chapter 15
Electrophilic Aromatic Substitution reactions (halogenation, nitration, FriedelCrafts alkylation and acylation, sulfonation)
Side chain oxidation with KMnO4
Birch reduction
Activating/Deactivating groups – directing tendencies
Benzylic radical halogenation, substitution, and elimination
Clemmensen reduction
Chapter 16
Nitrile, ester, and acyl halide reductions
Alcohol oxidations
Alkyne hydration
Dialkyl cuprate coupling
Grignard addition to carbonyls and nitriles
Hemiacetal and acetal (thioacetals) formation and hydrolysis
Cyanohydrin formation
Imine and enamine formation and hydrolysis
Wittig reaction
Baeyer-Villiger oxidation
Chapter 17
Keto-enol tautomerization
Enolate formation (kinetic and thermodynamic)
Enolate chemistry
o Racemization/epimerization
o Halogenation (haloform)
o Alkylation
Things to Know for the Final Exam
o Selenation/selenoxide elimination
o Aldol and aldol condensations
o Aldol cyclizations
α−β Unsaturated carbonyl chemistry
o Michael addition
o Conjugate addition of R2CuLi, HCN, R2NH, RSH
o 1,2-Addition of Grignard, RLi, and hydride
Chapter 18
Forming carboxylic acids (oxidations, hydrolysis, CO2 add’n to Grignard)
Acyl group activation (SOCl2, formation of anhydrides)
Ester synthesis (Fischer, Baeyer-Villiger)
Amide synthesis (amine add’n to acyl chloride, DCC coupling)
Amine synthesis (reduction of nitriles and imines – see Ch. 20 for more ways)
Ketone synthesis (alkyne hydration, cuprate addition to Nitrile, F-C acylation,
ozonolysis, oxidation)
Aldehyde syntheis (oxidation, ozonolysis, reduction of esters and acyl chlorides)
Nitrile synthesis (addition of cyanide, dehydration of amides)
Addition to carboxylic acids and derivatives
Relative reactivity of carboxylic acid derivatives
Chapter 19
Claisen, crossed Claisen, reverse Claisen and Dieckmann condensations
Tautomerization in b-Dicarbonyl compounds
Acetoacetic ester synthesis
Malonic ester synthesis
Direct alkylation/acylation with LDA
Reaction of enolates with carbonyls and unsaturated systems
Conjugate add’n to unsaturated dicarbonyl systems
Enamine alkylation and acylation
Umpolung chemistry with dithianes
Chapter 20
Synthesis of amines
o Amination of alkyl halides
o Reduction of azides, nitroaryls, imines (reductive amination), nitriles, oximes, and
o Gabriel synthesis
o Hofmann and Curtius rearrangements
Reactions of amines
Things to Know for the Final Exam
Act as bases and nucleophiles
Forming sulfonamides and amides
Hofmann and Cope eliminations
Chapter 21
Industrial phenol synthesis
Synthesis of phenol through diazonium salt
Reactions of phenols (acylation, alkylation, electrophilic aromatic substitution)
Other reaction – Nucleophilic Aromatic subs. Via SNAr and benzynes
Claisen rearrangement
Chapter 22
Naming and numbering sugars
Glycoside formation and hydrolysis
Oxidation and reduction of sugars
Forming ethers and esters with sugars
Chain shortening and lengthening
Acetonide formation and hydrolysis
Chapter 23
Steroid numbering
Reactions of fatty acids and triacylglycerols (see esters/acids and alkenes)
Terpene formation by coupling IPP and DMAPP
Chapter 24
Amino acid basics
Amino acid synthesis (ammonolysis of halo acids, Gabriel modification and
Strecker synthesis)
Protecting groups for amines and carboxylates (on and off)
Activating agents for coupling amino acids
Chapter 25
Nucleic acid basics
Coupling base to sugar
Phosphoramidite coupling
Protecting groups for hydroxyls (DMTr)