Alcohols

• Alcohols have a higher boiling point compared to alkane
• Factors affecting Acidity of Alcohols

  • Resonance
  • Induction
  • Solvation
• Preparation of Diol reagents

  A) H2/Pd

  B) LiAlH4

  C) NaBH4

  
• Reducing Agents of Alcohol

  • NaBH4 - weak
  • LiAlH4 - strong
  • H2/Pd - not common
• NaBH4 cannot reduce

  • carboxylic acid
  • ester
• conjugate base of alcohol

  A) Alkoxide

  
• Deprotonating reagents of alcohol (to alkoxide)

  • NaH
  • Na
  • Li
  • K
• Preparation of Diols

  A) RCO3H

  B) OsO4

  
• Grignard reagent

  1. RMgX
  2. H2O
• Preparation of Alcohols via Reduction

  A) NaBH4

  B) H2

  C) LiAlH4

  D) NaBH4

  E) H2

  F) LiAlH4

  G) LiAlH4

  H) LiAlH4

  
• Preparation of alcohols via grignard reagent

  A) RMgX

  B) RgMgX

  C) R

  D) R

  E) R

  
• Protection and de-protection of Alcohols

  A) TMSCl

  B) TBAF

  C) OTMS

  
• common protecting group that replaces an alcohol.

  OTMS
• reagents for conversion of alcohol to ROTMS

  TMSCl, Et3N
• SN1 reactions with alcohol

  A) HX

  
• SN2 reactions w alcohol

  A) HBr

  B) TsCl, py

  C) PBr3

  D) SOCL2

  E) HCl

  
• E1 E2 reactions w alcohol

  A) H2SO4

  B) TsCl

  C) NaOEt

  
• oxidation of alcohols and phenols

  A) Na2Cr2O7

  B) PCC

  C) DMP

  D) Na2Cr2O7

  E) Na2Cr2O7

  
• two common ways for removing a TMS protection group

  H3O+ or F-
• most common reagent for deprotection of alcohols from TMS

  TBAF
• intermediate in phenol synthesis characterized by an isopropyl group attached to benzene

  cumene

  
  

  by-product is acetone
• five reagents for primary alcohol to alkyl halide via SN2 reaction (2 for bromination, 2 for chlorination, one for general)

  • HBr
  • HCl, ZnCl2
  • 1. TsCl, py. 2. NaX
  • SOCl2, py.
  • PBr3
• Reagent for tertiary alcohol to alkene via an E2 mechanism

  1. TsCl, py
  2. Strong base
• Oxidation of Alcohol

  in primary alcohol, if reagent is too strong it reaches carbon dioxide

  A) aldehyde

  B) carboxylic acid

  C) ketone

  D) no reaction

  
• Strong ox. agents: K2Cr2O, K2CrO4, Jones' rgt, CrO3
• Weak ox. agent: PCC
• Swern Oxidation reagents and conditions

  • DMSO,(COCl)2 [oxalyl chloride]
  • Et3N
  • 78degC

  primary - aldehyde

  secondary - ketone
• Swern Oxidation

  A) DMSO

  B) Et3N

  
• Dess- Martin oxidation

  primary - aldehyde

  secondary - ketone

  A) DMP
• Oxidation of phenol


  reagents:

  • CrO3, H3O+, acetone
  • Na2Cr2O7, H2SO4, H2O

  
• Oxidation of Alcohol summary

  rectangle box - type n/a

  A) Na2Cr2O7

  B) PCC, DMP, DMSO

  C) aldehyde

  D) carboxylic acid

  E) ketone

  F) n/a

  G) Tertiary