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Chapter 12 1o OH 2o
OH 3o OH
Ethanol 2-Methyl-2-propanol
2-Propanol
Alcohols from (isopropyl alcohol) (tert-butyl alcohol)
Phenols
Carbonyl Compounds Compounds that have a hydroxyl group attached directly
to a benzene ring
Oxidation-Reduction &
Organometallic
Compounds
Examples OH OH
1B. Nomenclature of Ethers
OH
Rules of naming ethers
OH Similar to those with alkyl halides
2-Propanol 1,2,3-Butanetriol CH3O Methoxy
(isopropyl alcohol) CH3CH2O Ethoxy
Example
3-Propyl-2-heptanol O
8
OH Ethoxyethane
which is correct? 6
7
(diethyl ether)
1
2 3 4
5
6
7 or 5 4
3
2
1
OH OH
1
Physical Properties of Alcohols 6. Alcohols as Acids
Name Formula mp bp (oC) *
(oC) (1 atm) Alcohols have acidities similar to that of
Methanol CH3OH -97 64.7 inf. water
Ethanol CH3CH2OH -117 78.3 inf. pKa Values for Some Weak Acids
Isopropyl alcohol CH3CH(OH)CH3 -88 82.3 inf.
tert-Butyl alcohol (CH3)3COH 25 82.5 inf. Acid pKa
Hexyl alcohol CH3(CH2)4CH2OH -52 156.5 0.6 CH3OH 15.5
OH
CH3CH2OH 15.9
Ethylene glycol HO -12.6 197 inf.
(CH3)3COH 18.0
* Water solubility (g/100 mL H2O)
2014 by John Wiley & Sons, Inc. All rights reserved. 2014 by John Wiley & Sons, Inc. All rights reserved.
H2O & alcohols are the 4. Alcohols from Alkenes (from CHAPTER 8)
Relative Acidity
strongest acids in this series You know this !
H2O > ROH > RC CH > H2 > NH3 > RH OxymercurationDemercuration
OH OH
Hg(OAc)2 NaBH4
Increasing acidity C C C C C C
H2O, THF NaOH
HgOAc H
Markovnikov regioselectivity
Relative Basicity HO is the weakest Anti stereoselectivity
acid in this series
HydroborationOxidation
R > NH2 > H > RC C > RO > HO
Increasing basicity
Anti-Markovnikov regioselectivity
2014 by John Wiley & Sons, Inc. All rights reserved. Syn-stereoselectivity
PBr2
Br + R O R Br + HOPBr2
(63%) H
2
9. Alcohols with SOCl2 10. Tosylates, Mesylates, and Triflates:
O H O Leaving Group Derivatives of Alcohols
Cl
R O H + Cl S Cl R O S
Cl
O O
Cl
N +R O S Cl R O S N SN2 displacement of the mesylate or tosylate with a
nucleophile is possible
Cl OTs + Nu
O
O O
N + S R Cl + O S N
Nu + OTs
2014 by John Wiley & Sons, Inc. All rights reserved. 2014 by John Wiley & Sons, Inc. All rights reserved.
R OH Br
3
Example 3 11E. Silyl Ether Protecting OH groups
Synthesis of
2 4 6
Ph Na (Not Formed)
HO Ph
1 3
5 +
HO Ph
O
H I
2 4
from HO
1 3
I Instead
and Na Ph H Ph O
Ph Na +
6 5 +
O O
H I I
2014 by John Wiley & Sons, Inc. All rights reserved. 2014 by John Wiley & Sons, Inc. All rights reserved.
O + H Br O + Br
H
Br H
+ Br H
O O + Br
H
O
2014 by John Wiley & Sons, Inc. All rights reserved. H H + Br
4
13. Epoxides (OXIRANE) 13B. Stereochemistry of Epoxidation
Epoxide (oxirane)
o Addition of peroxy acid across a C=C
A 3-membered ring containing an oxygen
bond
13A. Synthesis of Epoxides:
Electrophilic Epoxidation
A stereospecific syn (cis) addition
peroxy oO o
C C C C
acid
MeOH +
RO O MeO OH
(protonated
C C + R O H
epoxide) H
OH o
This carbon resembles a 3 carbocation
2014 by John Wiley & Sons, Inc. All rights reserved. 2014 by John Wiley & Sons, Inc. All rights reserved.
5
If the epoxide is unsymmetrical, in the 15. Anti 1,2-Dihydroxylation of
base-catalyzed ring opening, attack Alkenes via Epoxides
by the alkoxide ion occurs primarily at
Synthesis of 1,2-diols
the less substituted carbon atom
EtO
Et O +
O O
o
1 carbon atom is
less hindered
2014 by John Wiley & Sons, Inc. All rights reserved. 2014 by John Wiley & Sons, Inc. All rights reserved.
OH H2O O O O O
O O
O
O
OH
(18-crown-6) (15-crown-5) (12-crown-4)
2014 by John Wiley & Sons, Inc. All rights reserved.
O O O
O Me
O Me O
Me
Me O O O
O O OH
1. 1. BH3 THF
O Me Me 2. H2O o 2. H2O2, NaOH
(1 alcohol)
Nonactin MgBr
2014 by John Wiley & Sons, Inc. All rights reserved. 2014 by John Wiley & Sons, Inc. All rights reserved.
6
Reaction of alcohols Synthesis of ethers
OR
Br conc. H2SO4
R O R
RO 140oC
1. base
PBr3 2. R-X
R X R OH
OH
Cleavage reaction of ethers
SOCl2 (1o alcohol)
H X X
Cl R O R' R O R' ROH + R'X
H
2014 by John Wiley & Sons, Inc. All rights reserved. 2014 by John Wiley & Sons, Inc. All rights reserved.
7
3A. Lithium Aluminum Hydride Mechanism
O H O
O 1. LiAlH4, Et2O OH
(1) + H Al H R OR'
R OH 2. H+, H2O R H R OR'
H H H
O
O 1. LiAlH4, Et2O OH R'O +
(2) + HOR' R H
R OR' 2. H+, H2O R H H
H
O H Al H
OH O
O 1. LiAlH4, Et2O OH H H H
(3) R H R H
R H 2. H+, H2O R H H H
H
Esters are reduced to 1o alcohols
2014 by John Wiley & Sons, Inc. All rights reserved. 2014 by John Wiley & Sons, Inc. All rights reserved.
3B. Sodium Borohydride (less reactive) 3C. LiAlH4 versus NaBH4 Reactivity
O NaB H 4 OH
(1 )
H
reduced by LiAlH4
R H H 2O R
H
O OH
NaB H 4 reduced by NaBH4
(2 )
R R' H 2O R R' O O O O
H
< < <
H O
O R O R OR' R R' R H
+ H B H R R' ease of reduction
+
R R' H
H
Mechanism
O
Aldehydes are OH H H
reduced to 1 alcohols
& ketones are R'
reduced to 2 alcohols R
H
Swern oxidation of a 1
alcohol to an aldehyde
Swern oxidation of a 2
alcohol to a ketone
2014 by John Wiley & Sons, Inc. All rights reserved.
8
4C. Chromic Acid (H2CrO4) Oxidation Jones oxidation
Reagent: CrO3 + aqueous H2SO4
A Cr(VI) oxidant
CrO3 O
R OH + Cr(III)
H2SO4
R OH
(orange solution) (green)
Chromic acid (H2CrO4) usually prepared OH CrO3 O
+ Cr(III)
by [CrO3 or Na2Cr2O7] + aqueous H2SO4 H2SO4
R R' R R'
(orange solution) (green)
OH
Jones reagent CrO3
No Reaction
R" H2SO4
R
2014 by John Wiley & Sons, Inc. All rights reserved.
R' 2014 by John Wiley & Sons, Inc. All rights reserved.
CrO3 O
A R OH + Cr(III) 4E. Potassium Permanganate (KMnO4)
H2SO4
Chemical (orange solution)
R OH
(green)
Test for OH CrO3 O
Primary + Cr(III)
H2SO4
R R' R R'
and (orange solution) (green)
OH
Secondary CrO3
No Reaction
Alcohols R R" H2SO4
R' 5. Organometallic Compounds
Compounds that contain carbon-metal bonds are called
organometallic compounds
+
PCC = [CrO3Cl] C M C : M C M
N
H
primarily ionic primarily covalent
(Pyridinium chlorochromate)
(M = Na or K) (M = Mg or Li) (M = Pb, Sn, Hg or Tl)