Final: Topic 1 Flashcards
EArS: Sulfonation
Benzene + H2SO4 + SO3
=> Benzene-SO3H
EArS: Halogenation
Benzene + FeX3 + X2
=> Benzene-X
EArS: Nitration
Benzene + H2SO4 + HNO3
=> Benzene-NO2
EArS: Friedel Crafts Acylation
Benzene + AlCl3 + R-Cl=O
=> Benzene=O-R
EArS: Friedel Crafts Alkylation
Benzene + AlCl3 + RCl
=> Benzene-R
Clemmensen Reduction
Used to reduce acylation products to avoid rearrangements from alkylation
Zn/Hg, HCl, reflux
Wolff-Kischner Reduction
Used to reduce acylation products to avoid rearrangements from alkylation
H2NNH2, KOH, heat (delta)
KMnO4, OH-, H3O+ against a ketone - -
Oxidizes to a carboxylic acid
Diazonium:
NaNO2, HX, benzyl amine
Creates diazonium ion (+1): benzyl-N—N
Grignard addition to ketones:
Ketone + 1) R’MgBr, ether 2) H3O+
3° Alcohol with R, R’ and R’’ groups from ketone and R’MgBr
Grignard addition to esters:
Ester + 1)R’MgBr, ether 2) H3O+
3° alcohol with R, R’ and R’ groups + R’‘OH
Addition of primary amines:
Carbonyl group + RNH2
Creates imine: (C=N-R) + H2O
Addition of secondary amines: Carbonyl group (H-C-C=O) + R2NH
Creates enamine: R
C=C-N+R and H2O
Addition of hydroxylamine:
Carbonyl group + NH2OH
Creates oxime: C=NOH + H2O
Conjugate addition of organocuprates:
Carbonyl (C=C-C=O) + 1) R2CuLi 2)H3O+
R-C-C-C=O
H
Carboxylation of Grignard Reagents:
RMgBr + 1) CO2, ether 2) H3O+
Creates ester: OR’
R-C=O
Reduction of Nitriles to amines:
RC=N + 1) LiAlH4 2) H3O+
R-C-NH2
H H
Baeyer-Villiger Oxidation:
Ketone + mCPBA R-C=O-O-OH
Creates Ester:
R-C=O-O-R’
Carboxylic acids to acid chlorides:
Carboxylic acid + SOCl2, CHCl3
Creates acid chloride, SO2, HCl
Carboxylic acids to esters:
Carboxylic acid + R’OH + acid cat.
Creates ester w’ R’ + H2O
Alcoholysis of acid chlorides to esters:
Acid chloride + R’OH
Creates ester + HCl
Aminolysis of acid chlorides to amides:
Acid chloride + 2 NH3
Creates amide + NH4Cl
Hydrolysis of esters to acids:
Ester + H3O+ or NaOH
Creates carboxylic acid + R’OH
Transesterification:
Ester + R’‘OH + acid cat.
Creates ester with R’’, and R’OH
Grignard Reaction with amides:
Amide + R’MgX + H3O+
Creates ketone
Nucleophilic Aromatic Substitution:
O2N-Benzene-F + NaSR, DMF
Creates O2N-Benzene-SR + NaF
Reduction: Aldehyde
Aldehyde + 1) NaBH4 2) H3O+
Creates 1° Alcohol: R-C-OH
Reduction: Ketones
Ketone + 1)NaBH4 2) H3O+
Creates 2° Alcohol: R-C-R’
OH
Reduction: Esters
O=C-OR + 1) LiAlH4 2)H3O+
Creates 1° Alcohol: R-C-OH + R’‘OH
Tautomerization
=O to -OH in an enol, by -OH or H3O+,
Halogenation of Aldehydes/Ketones
X2, Acid or Base, adds one X in alpha position
Haloform Reaction
X3, OH- and H2O, creates -CX3 and then -O- and HCX3
Halogenation of Carboxylic Acids
PX3 for Acid chloride, then X2 to add a secondary X, then H2O to return to carboxylic acid
Alternative: P, X2, H2O to add one X to non- OH side of carboxylic
Alkylation of Ketones/Aldehydes
- LDA, THF, -78°C -> to move double bond and create O- (carboxylate anion)
- R’‘-X to finish alkylation and restore =O
Alkylation of Esters
- LDA, THF, -78°C (creates alpha anion)
2. R’‘-X
Alkylation of beta-keto esters (Acetoacetic ester synthesis)
- NaOEt, R-Br
- OH-/heat, H3O+, heat
- tBuOK, R’-Br
- OH-, H3O+, heat
Stork Enamine Synthesis (Alkylation of Enamines)
R’’–Br, H2O, heat
Claisen Condensation
Ester + 1. NaOEt, another ester, 2. H3O+
Adds from OEt side of ester to alpha position
Aldol Condensation 1
2 Aldehydes, NaOH, H2O
Aldol Condensation 2
Aldehyde + ester, LDA, -78°C, NH4Cl, creates 3° Alcohol in alpha carbon with R’ groups
