Download Chem 400 Review Chem 350 JJ.S17

1. Alcohols, Phenols, Oxidation and Reduction
 Alcohols are names with the suffix –ol
 The acidity of an alcohol/phenol can be assessed using its conjugate base: Consider
Atomic size/Electronegativity, Resonance, Induction, Orbital Type (ARIO)
 Electron withdrawing substituents stabilize conjugate bases while electron donating ones
destabilize a conjugate base
 Alcohols preparation: via SN1, SN2, hydration, and Grignard (MgBr-[C…]) mechanisms
 Reduction: H2 with Pt/Pd, NaBH4 and LiAlH4 (more reactive, can be used for esters). Need
quenches for NaBH4 and LiAlH4
 Oxidation: CrO3, H+/Na2Cr2O7, H+ (Joan’s reagents – strong oxidizers – will lead to
carboxylic acid product) and PCC (mild oxidizer – will only lead to ketone/aldehyde
products)
2. Dienes, Dienophiles, Diels –Alder Mechanism
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Diene: has conjugated pi bonds
Dienophile: must have at least one pi bond
s-trans = more stable conformer, but diene must be able to
assume s-cis conformation to participate in a Diels-Alder rxn
3. Benzene Derivatives and Rules of Aromaticity
Aromaticity: Cyclic, sp2 at each atom, 4n+2 pi electrons (Huckel’s Rule), planar
4. Electrophilic Aromatic Substitution (EAS) & Nucleophilic Aromatic Substitution (NAS)
EAS and NAS mechanisms maintain aromaticity.
NAS: Need a strong nucleophile, a good leaving
group and a strong EWG ortho/para to the LG
5. Ethers and Epoxides
 Williamson Ether synthesis: 1. Attack with NaH (:H- = strong base/nuc) 2. SN2 with
alkyl halide (has to be 1° or 2° and sp3)
 Epoxide preparation is achieved with m-chloroperoxybenzoic acid (mCPBA)
6. Aldehydes, Ketones and Nucleophilic Addition Reactions
 Aldehydes end with the suffix –al
 Ketones end with the suffix –one
 Aldehydes are more reactive than ketones because of sterics and electronics (Aldehydes
are connected to 1 EDG alkyl group while ketones are connected to 2)
7. Reactivity of Carboxylic Acids, Esters, and Amines and Named Mechanisms
 Preparation of Carboxylic Acid: 1. NaCN 2. H3O+ or 1. Grignard 2. CO2
 Keto-enol tautomers are constitutional isomers
 Keto = significantly more stable conformer – acts as an electrophile
 Enol = least stable conformer – acts as a nucleophile
 NaOH = best base for aldol condensation reaction