Chem 239 Reactions Flashcards
Oxidation of alcohols
weak: to ketone, PCC
strong: to COOH, KmnO4
Alkylbenzenes
to alkylate: R-Cl with AlCl3
To add carboxylic acid: KMnO4/H+
Grignard with Co2
Brominate benzene with Br2/FeBr3, remove Br with Mg, add CO2 and H3O+
Forms carboxylic acid
Acid chloride synthesis
SOCl2 or PCl5, COOH to COCl
Amide synthesis
Anhydride synthesis
Two carboxylic acids + heat
Decarboxylation reaction
Acid catalyzed esterification
carboxylic acid + R-OH-> Ester
Carboxylic acid reduction
Ester hydrolysis
RCOOR+H3O+->COOH
Lactonization
H+
Saponification
Ester-> carboxylic acid with carboxylate intermediate
Reagent: NaOH, then H+ workup
Acid catalyzed transesterificstion
Amide hydrolysis
H2O
amide> carboxylic acid
Acid chloride hydrolysis
H2O
acid chloride-> carboxylic acid
Ester reduction
LiAlH4
Amide reduction
LiAlH4+
RCONH2->R-NH2
Reaction of esters with grignard
ester->
Keto enol tautomerizarion
Acid catalyzed enolization
H3O+
Base catalyzed enolization
OH-
Malonic ester synthesis
Use NaOet and r-Br group of choice to turn a-carbon into nucleophile
Acetoacidic ester synthesis
Use NaOet and r-Br
Haloform reaction
excess X2, NaOH, , mild acidic workup
CHX3 formed, becomes leaving group
Aldol condensation
Addition: NaOH, H2O
condensation: heat, creates alkene
Intramolecular claisen
use NaOH
Conjugate addition
1,2/1,4 additions
Michael addition
KOH, Alkene, H2O
OH deprotonates, carbanion attacks, H grabbed
Robinson annulation
Start with Michael addition:
KOH, Alkene, H2O
OH deprotonates, carbanion attacks, H grabbed by alkene
Then: Base grabs a-hydrogen, intramolecular reaction, O- protonated and kicked off
Gabriel synthesis
KOH
H2NNH2
Reductive amination
H+, NaBH3CN
Amines via reduction
Amide or nitrile-> amine using LiAlH4 and H3O+
Hofmann elimination
R-NX3->alkene using Ag2O and heat
EAS with arylamines
aniline + (CH3CO)2O/pyridine -> Acetanilide
Nitrosations
No2 + HCl->N=O
N=O attacks NH2 on aryl amine
Reactions with Aryl diazonium salt
Ph-NH2 w/ HNO2 and H+-> Ph-N=-N
Mutarotation
Mechanism: H3O+ or OH- open hemiacetal, internal rotation of carbonyl, H3O+ or OH- closes hemiacetal
Isomerization of aldoses/ketoses
Glycosides
monosaccharides + alcohols in acid give cyclic acetals (one OH group->OCH3)
- to return to OH, use H3O+
Ether and ester derivatives of carbohydrates
Oxidation of carbs
Strong: HNO3 used, Turns first and last carbon to carboxylic acid
Weak: Br2, water, Turns CHO on top to carboxylic acid
Reduction of carbs
NaBH4
turns top COH to CH2OH
Epimerization
NaOH and H2O
Killiani Ester Synthesis
- HCN
- H2, Pd/BaSO4
- H3O+
Just adds extra carbon
claisen condensation
Two esters + EtOH/HCl
makes acetoacetic ester
periodate oxidation
OH groups turned into aldehyde
To turn diazonium into other things
CN: CuCN
Br: CuBr
Cl: CuCl
To add NO2 group to benzene
HNO3 and H2SO4
To turn nitro group into an amine
H2, Pd
ketone to carboxylic acid
NaOH, Br2, H3O+