Professional Documents
Culture Documents
Organic Chemistry
Two credits
Second Semester 2009
Chapter 10
Hydration of alkenes
Hydroboration-oxidation of alkenes
Hydrolysis of alkyl halides
Syntheses using
Grignard reagents
organolithium reagents
Sources
Sourcesof
ofalcohols
alcohols
R R
C O H C OH
H H
Example:
Example: Catalytic
CatalyticHydrogenation
Hydrogenation
O
CH3O CH + H2
Pt, ethanol
CH3O CH2OH
(92%)
Reduction
Reductionof
ofKetones
KetonesGives
GivesSecondary
SecondaryAlcohols
Alcohols
R R
C O H C OH
R' R'
Example:
Example: Catalytic
CatalyticHydrogenation
Hydrogenation
O H OH
Pt
+ H2
ethanol
(93-95%)
Metal
MetalHydride
HydrideReducing
ReducingAgents
Agents
H H
+ – + –
Na H B H Li H Al H
H H
Sodium Lithium
borohydride aluminum hydride
Aldehyde
O2N O2N
O NaBH4
CH CH2OH
methanol
(82%)
Ketone
O NaBH4 H OH
ethanol
(84%)
Lithium
Lithiumaluminum
aluminumhydride
hydride
Aldehyde
O 1. LiAlH4
diethyl ether
CH3(CH2)5CH CH3(CH2)5CH2OH
2. H2O
(86%)
Ketone
O 1. LiAlH4 OH
diethyl ether
(C6H5)2CHCCH3 (C6H5)2CHCHCH3
2. H2O
(84%)
Preparation of Diols
Diols
Diolsare
areprepared
preparedby...
by...
O O
H2 (100 atm)
HCCH2CHCH2CH
Ni, 125°C
CH3
HOCH2CH2CHCH2CH2OH
CH3
3-Methyl-1,5-pentanediol
(81-83%)
Hydroxylation
Hydroxylationof
ofAlkenes
Alkenes
Gives
GivesVicinal
VicinalDiols
Diols
C C
C C
HO OH
C C
O O
Os
O O
Just for general knowledge, will not be tested on
Just for general knowledge, will not be tested on
Example
Example
CH3(CH2)7CH CH2
(CH3)3COOH
OsO4 (cat)
tert-Butyl alcohol
HO–
CH3(CH2)7CHCH2OH
OH
(73%)
Reactions of Alcohols
Review
Reviewof
ofReactions
Reactionsof
ofAlcohols
Alcohols
RCH2O CH2R
H OH
H+
RCH2O CH2R + H OH
acid-catalyzed
referred to as a "condensation"
equilibrium; most favorable for primary alcohols
Example
Example
2CH3CH2CH2CH2OH
H2SO4, 130°C
CH3CH2CH2CH2OCH2CH2CH2CH3
(60%)
Mechanism
Mechanismof
ofFormation
Formationof
ofDiethyl
DiethylEther
Ether
Step 1:
•• •
CH3CH2O • H OSO2OH
H
H
+ –
CH3CH2O •• + OSO2OH
H knowledge, will not be tested on
Just for general
Mechanism
Mechanismof
ofFormation
Formationof
ofDiethyl
DiethylEther
Ether
Step 2:
H H
CH3CH2
CH3CH2 ••
+O
+ + •• O ••
+•
H CH3CH2O •
H
•• •
CH3CH2O • H
Step 3:
CH3CH2 CH3CH2
+•
CH3CH2O • CH3CH2O •• +
••
H
••
•• OSO ••
2OH H OSO2OH
– •• ••
CH3OCH2 CH3
diethyl ether
Functional
FunctionalClass
ClassIUPAC
IUPACNames
Namesof
ofSulfides
Sulfides
CH3SCH2 CH3
SCH3
ethyl methyl sulfide
diethyl sulfide
Names
Namesof
ofCyclic
CyclicEthers
Ethers
O O O
Oxirane Oxetane Oxolane
(Ethylene oxide) (tetrahydrofuran)
O O
Oxane 1,4-Dioxane
(tetrahydropyran)
Just for general knowledge, will not be tested on
Names
Namesof
ofCyclic
CyclicSulfides
Sulfides
S S S
Thiirane Thietane Thiolane
S
Thiane
Just for general knowledge, will not be tested on
Structure and Bonding
in
Ethers and Epoxides
O O
H H CH3 H
105° 108.5°
O O
CH3 CH3 (CH3)3C C(CH3)3
112° 132°
An
Anoxygen
oxygenatom
atomaffects
affectsgeometry
geometryin
inmuch
muchthe
the
same
sameway
wayasasaaCH
CH22group
group
boiling point
OH 117°C
Ethers
Ethersresemble
resemblealcohols
alcoholsmore
morethan
thanalkanes
alkanes
with
withrespect
respectto
tosolubility
solubilityin
inwater
water
very small
Hydrogen bonding to
7.5 water possible for ethers
O
and alcohols; not
possible for alkanes.
OH 9