OChem2Ch13

• Name as standard alkene/alkyne
• Replace -e with -ol and indicate the position of the C containing the O
• example - 2-hexanol

• Boiling point much higher than similar MW hydrocarbons due to H bonding
• Low MW alcohols miscible in water, pentanol+ are not

• Alcohol is on the acidic side, but not highly acidic
• Strong Base: Need a strong base OR base that can't form equilibrium (NaH, the H₂ will evaporate)
• Na, Li, K: Also cause the H₂ to evaporate
• Phenol is much more acidic than other alcohols (conj base highly stablized)
• NaOH will deprotonate phenol

• 1. Resonance:
• 2. Induction: highly electronegative groups
• 3. Solvation effects: Solvent helps to stabilize (less substituted alcohol will be more stabilized - steric hinderence)

• RCH₂Cl + NaOH --S_N2-> RCH₂OH + NaCl
• RC(CH₃)₂Cl + H₂O --S_N1-> RC(CH₃)₂Cl + HCl

2° alkyl halides do not work well (SN1 too slow, SN2 favors elimination)

• CH₃-CH=CH₂ undergoes the following rxns..
• Markovnikov
• H₂SO₄,H₂O: CH₃-CH(OH)-CH₃
• 1)Hg(OAc)₂,H2O 2)NaBH₄: CH₃-CH(OH)-CH₃
• Anti-Markovnikov
• 1)BH₃*THF 2)HOOH, NaOH: CH₃-Ch₂-Ch₂-OH

• Oxidation: addition of bonds to O OR removal of bonds to H (oxidation # increases)
• Reduction: addition of bonds to H OR removal of bonds to O (oxidation # decreases)
• Oxidation #: Count e- around atom vs valence (which atom is more electronegative?)

• Ketone --red-> 2° alcohol
• Aldehyde --red-> 1° alcohol
• Formaldehyde --red-> methanol

• Reducing agents:
• Will reduce C=O and C=C:
• H₂ in presence of catalyst
• Selective.  Will reduce C=O and leave C=C:
• NaBH₄ in EtOH, MeOH, or H₂O
• LAH is much more reactive than NaBH₄ but VERY water sensative (no protic solvents), requires 2 steps

• RCOOH
• 1) LAH, ex 2)H₂O: R-CH₂OH
• NaBH4: no rxn
• RCOOR
• 1) LAH, ex 2)H₂O: R-CH₂OH + HOR
• NaBH4: no rxn

• Must include chain with both OH groups
• Name as alkane -e +diol
• Example - 2,3-hexanediol

• From diketones:
• H₂,Pt: diol
• 1)LAH 2)H2O: diol
• 1)NaBH4 2)MeOH: diol

• From alkene
• OsO₄,NMO: cis diol [syn addition]
• 1)RCO₃H 2)H₂O: trans diol [anti addition]

• R-X --Mg->  R-Mg-X
• Ph-Br --Mg-> Ph-Mg-Br
• *C-Mg bond gives C a negative charge which attacks the C=O of ketones/aldehydes
• Product is an alcohol + R group.  VERY IMPORTANT
• Water must be added separately (even moisture will destroy the gignard reagant).
• ketone: 3° alcohol + R (same C)
• aldehyde: 2° alcohol + R (same C)
• Ester: 3° alcohol + R + R (same C)
• Carboxillic acid: WILL NOT WORK (protic)

*Grignard can't form if OH is on the attempted reagent

• 1. Remove the H from OH group, replace with "protecting group" that will allow Grignard reagent to form
• RO-H --TMSCl,Et3N-> RO-TMS
• 2. Form Grignard reagent, perform rxn
• 3. Deprotect, converting protecting group to -OH again
• RO-TMS --H₃0⁺ OR F^--> RO-H

*F^- typically donated by TBAF

• 1°OH
• HBr: 1°Br + H2O (SN2)
• HCl, ZnCl2: 1°Cl + H2O (SN2)
• SOCl2,py: 1°Cl (SN2)
• PBr3: 1°Br (SN2)

• 2°OH
• 1)TosCl, pyrimidine 2)NaBr: 2°Br (inversion of config) (SN2)
• SOCl2,pyrimidine: 2°Cl  (inversion of config) (SN2)
• PBr3: 2°Br (inversion of config) (SN2)

• 3°OH
• HX: 3°X + H2O (SN1)

• 3°OH
• H2SO4: 2x bond where C-OH was (E1)
• 1)TosCl,Et3N 2)NaOEt,EtOH: 2x bond where C-OH was (E2)

• 1° Alcohol -> Aldehyde -> Carboxylic acid
• 2° Alcohol -> Ketone
• 3° Alcohol -> N/A

H₂CrO₄ OR H₂Cr₂O₇,H₂SO₄,H₂0 OR CrO₃,H₃O+ will perform a full oxidation

PCC,CH2Cl2 can perform a single-step oxidation