CHM 256 Final

aldehyde + H2CrO4

oxidized into carboxylic acid and carbonyl

aldehyde + Ag2O (OR) NaClO2

oxidized into carboxylic acid

ketone tautomers

keto tautomerized into enol

aldehyde tautomers

keto (major) and enol (minor)

ketones are more acidic than alkanes because

1. enolates are resonance-stabilized

2. carbonyl has strong inductive effect

3. enols are electronically similar to alcohols

enolates formed by strong bases (LDA, NaH)

reaction is irreversible

enolates formed by weaker bases (NaOR, NaOH)

reaction is reversible

enolate + D₂O →

addition

enolate + Br₂ →

halogenation

enolate + alkane →

alkylation

enolate + aldol → (WU)

aldol addition

enolate + ester → (NaOR & ROH, then acidic WU)

Claisen condensation

enolate + 1,4 carbonyl alkene → (WU)

phenol + K₂Cr₂O₇ & H₂SO₄ →

para quinone

para position phenol + K₂Cr₂O₇ & H₂SO₄ →

para quinone

ortho position phenol + K₂Cr₂O₇ & H₂SO₄ →

ortho quinone

reducing quinones back to phenols

Na₂S₂O₄ & H₂O

excess amine + alkyl halide →

SN2 rxn, then A/B rxn → 2° aliphatic to 3° aliphatic

halide + sodium azide (NaN₃) → 1. LiAlH₄ 2. H₂O →

reduced to primary amine

molecules with 4n + 2 pi electrons are

aromatic

molecules with 4n pi electrons are

antiaromatic

molecular orbitals at lower energy than atomic orbitals are called

bonding

molecular orbitals at higher energy than atomic orbitals are called

antibonding

molecular orbitals at equal energy than atomic orbitals are called

nonbonding

coenzyme Q

carrier of electrons in oxidative phosphorylation, anchored to the mitochondrial membrane

menadione

synthetic Vitamin K replacement

alkane pKa

~50

Ester pKa

23-25

Ketone pKa

20-22

Aldehyde pKa

17-19

Alcohol pKa

16-17

HDA (from LDA) pKa

35

water pKa

15.7

malonate pKa

13

Strong base and large molecule

LDA

Strong base but small molecule

NaH

Weaker base

NaOH or NaOR