Organic Named Reactions Flashcards
How do you add a hydroxyalkyl to a ketone?
Aldol reaction
Aldehye + Ketone under basic or acidic conditions
How do you convert a ketone to an ester and cyclic ketones to lactones?
Baeyer-Villiger Oxidation
Peracids (MCBPA) or hydrogen peroxide + lewis acid
Regiospecificity of the reaction depends on migratory ability - more e- donating is faster
How do you convert an aryl amine to aryl fluroides?
Balz-Schiemann
Diazonation with HBF4 and NaNO2 then thermal or photochemical decompsotion
How do you convert an oxime to an amide?
Beckmann rearragement
H2SO4 conc and heat
Can be used as a ring expansion technique
How do you convert a β-ethylamines bonded to an e- rich arenes to quinoline derivative?
Bischler-Napieralski Reaction
Forms 3,4-dihydroisoquinolines
Uses POCl3 and heat in toluene
How do you cause the disproportionation of non-enolizable aldehydes to carboxylic acids and alcohols?
Cannizzaro reaction
Uses KOH
How do you aminate a subsituted pyridine?
Chichibabin reaction
Uses NaNH2 / NH3, heat and H2O
How do convert esters with α-hydrogen to a β-ketoester?
Clasien condensation
Sodium alkoxide then H3O+
Driving force is formation of stabilised anion of β-ketoester
How do you form a α,β-epoxy ester from a carbonyl compound?
Darzens condensation
Carbonyl + α-halo ester in presence of base
How can you cause an intramolecular condensation of a diester?
Dieckmann condensation
Sodium alkoxide then acidic workup
Produces 5- or 6- membered cyclic β-keto ester
How can you convert a cyclopropanones to carboxylic acid or derivatives?
Favorskii rearrangement
Base-catalysed
cyclopropanones themselves made from basic reaction of reaction of α-halo ketones
How do you convert a carboxylic acid and alcohol to ester?
Fischer esterification
Equilibrium - lewis or bronstead acid catalysed
How do you add a acyl group to a benzene or aryl ring?
Friedel-crafts acylation
Electrophilic aromatic substiution
Require lewis acid catalyst
How do you add a alkyl group to a benzene or aryl ring?
Friedel-Crafts alkylation
Needs alkyl halide
Electrophilic aromatic substiution
Require lewis acid catalyst
How do you convert a primary alkyl halide into a primary amine?
Gabriel synthesis
Pottasium phthalimide (-NH2 synthon, which is acidic) then base or hydrazine
How do you formylate a benzene?
Gatterman-Koch
CO + HCl then add AlCl3 and benzene
Not applicable to phenol / phenol ethers
How do you convert a carboxylic acid to acyl bromides and α-bromo acids?
Hell-Volhard-Zelinsky reaction
Br2 & PBr3 catalyst
How do you convert a primary amide to form the corresponding primary amine?
Hofmann rearrangement
Br2/Cl2 and strongly basic NaOH (aq)
Goes via isocyanate intermediate
How do you convert a ketone/aldehyde to an α,β-unsaturated compounds?
Knoevenagel condensation - modification on aldol
Activated compound (e- withdrawing containing) with 2xH on a C with a weakly basic amine
How do you synthesise a substituted pyrrole?
Knorr pyrrole synthesis
α-amino-ketone and carbonyl with EWG α like an ester
Zinc and acetic acid catalysis
α-amino-ketone produced in situ with oxime via Neber
How do you convert a oxime to an α-amino-ketone?
Neber rearrangement
TsCl then base
Beckmann rearrangement is side reaction
How do you convert a primary halide to an aldehyde?
Kornblum oxidation
DMSO then Et3N
via alkoxysulfonium ion
How do you convert a organic peroxide to corresponding ketone and alcohol?
Kornblum-DeLaMare rearrangement
Base (KOH/Et3N) or Acid catalysis
How do you amino alkylate an acidic proton α to a carbonyl?
Mannich reaction
1°/2° amine or ammonia & formaldehyde
How do you cause a hydride shift from the α-carbon of an alcohol component to the carbonyl carbon of a second component ?
Meerwein-Ponndorf-Verley (MPV) reduction
Aluminium alkoxide + alcohol + carbonyl
Highly chemoselective
How do you convert 1°/2° alcohols to esters/thioesters?
Mitsonobu reaction
DEAD/DIAD & Ph3P with carboxylic acid
How can you cause a cationic [1,2]-sigmatropic rearrangements of a C in bicylic terpenes?
Nametkin rearrangement
Acid catalysed
Goes via non-classical carbocation
How do you synthesise a substituted furan?
Paal-Knorr Furan synthesis
Cyclization of 1,4-dicarbonyl compounds using H+
How do you produce a pyrrole from 1,4-diketones?
Paal-Knorr pyrrole synthesis
1,4-diketones + 1° amine
How do you produce a substituted thiophene?
Paal-Knorr thiophene synthesis
1,4-diketones + P4S10
How do you isomerize 2,3-epoxy alcohols with inversion of config?
Payne rearrangment
Basic conditions (aq)
Causes migration of the epoxy group
How do you convert an aromatic aldehyde to an α,β-unsaturated aromatic acid?
Perkin reaction
Aromatic aldehyde + Acid anhydride & Alkali salt
How do you convert α-silylcarbanions to alkenes?
Peterson Olefination
Add carbonyl then either base or acid
Base makes concerted syn elimination and acid causes anti elimination
How do you convert a β-arylenylamine to a tetrahydroisoquinoline?
Pictet-Spengler reaction
Add aldehyde/ketone with acid catalyst
Similar mechanism to mannich reaction
Driving force is electrophilicity of the iminium ion
How do you convert a 1,2-diol to a carbonyl?
Pinacol rearrangement
Acidic conditions
Can be used as a ring-expansion or contraction reaction
How can you rearrange an alkyl sulfoxide to a α-acyloxy–thioether?
Pummerer rearrangement
Acetic anhydride
How do you convert a α-halosulfones into E or Z alkenes?
Ramberg-Backland reaction
Z from weak bases, E from strong bases
How do you condense aldehydes/ketones to β-hydroxy-esters?
Reformatsky reaction
α-halo esters with Zinc in tolune then H3O+
How do you form a six-membered ring in a polycyclic compound?
Robinson annulation
Ketone + methyl vinyl ketone with base
How do you form an oxazole?
Robinson-Gabriel synthesis
2-acylamino-ketone intermolecular reaction in acidic conditions
How do you convert an alkene to a cyclopropane?
Simmons-smith
Reagents: CH2I2 + Zn
