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Alcohols and Ethers Prof. Dr. Adel Zamri, MS, DEA DEPARTMENT OF CHEMISTRY FACULTY OF MATHEMATICS AND NATURAL SCIENCES UNIVERSITY OF RIAU PEKANBARU 2013
Alcohols and EthersProf. Dr. Adel Zamri, MS, DEA
DEPARTMENT OF CHEMISTRYFACULTY OF MATHEMATICS AND NATURAL SCIENCES
UNIVERSITY OF RIAUPEKANBARU
2013
Introduction
Alcohols
Ethers
Medicinal Research
Anesthetic
Nomenclature
Nomenclature of Alcohol:
To learning the others nomenclature of alcohol, please watch the video of nomenclature that have been given and use the ChemDraw Software to help you!
Nomenclature of Ethers:
To learning the others nomenclature of ethers, please watch the video of nomenclature that have been given and use the ChemDraw Software to help you!
Physical Properties
Physical Properties of Alcohol and Ether:
Methanol
Ethanol
Ethylene Glycol
Diethyl ether
Reactions of Alcohols and Ethers
Review SN2 Reaction...
Preparation of Alcohol
From Alkene: Acid Hydration
In aquaeus acid solution:
Why not like this?
Write the mechanism of reaction below!
Hydroxylation of alkene
Mechanism:
Oxymercuration-demercuration
Reaction Step:
Mechanism:
Write the mechanism of reaction below!
Hydroboration
Answer the question below!
Syn-dihydroxylation
Reagents : KMnO4, -OH, or better:
OsO4 is reduced to OsVI.
OH
OH1. OsO4
2. H2S, H2O
Cis-1,2-cyclohexanediol
Gives complementary stereochemistry to anti-dihydroxylation
OsO
O O
O
VIII
Mech.:
C
COs
O
O O
O VIII
C
COs
O
O O
O VI
Osmate ester
H2O
C
C
OH
OH+ Os
O
HO O
HOCan be reoxidized by added oxidant, therefore can be made catalytic in Os
Other oxidants: H2O2 ; Fe3+; and catalytic OsO4
N
O
O CH3+-
Good because Os is expensive; OsO4, H2S are toxic.
Six electron TS
VI
Permanganate Hydroxylation
Exercise
Anti Hydroxilation
Learn this reaction!
Learn this reaction!
Learn this reaction!
Reactions from Alcohol
Displace hydroxy with halogen using TsCl (Tosyl Clhoryde)
Conversion of alcohols to alkyl halides
Mechanism:
How about Primary Alcohols and methanol?
Predict the product and write the mechanism!
Other ways to displace hydroxy with halogen : using PBr3
Other ways to displace hydroxy with halogen : using SOCl2
Pyridine as solvent
Learn the mechanism!
Learn the mechanism!R
OH
OHR
O
H+
SOCl2
ROH
PBr3
ROH
F3CSO2Cl
ROH
Ts-Cl
ROH2
X RX
RBr
RO
RO
ClR
O
Ts X RX
+ SO2 + HCl
SO2CF3 X RX
ROH
SOCl2 RCl + SO2 + HCl
Other way to displace hydroxy with halogen: using ZnCl2
Starting with alcohol, outline a synthesis of each of the following:a. Benzyl bromideb. Cyclohexyl chloridec. butyl bromide
Dehydration of Alcohol: Synthesis Alkene
Dehydration with rearangement
Preparation of Ethers
The Williamson Ether Synthesis
Solvomercuration-demercuration
Alcohols and Ether from Epoxide
Reactions from Ethers
HBr excess condition:
Examination
Nomenclature, substitution and elimination of alcohols
Nomenclature
Reaction and Synthesis
Predict the product of reaction below!
Predict the product of reaction below!
Predict the product of reaction below!
Oxidation and Reduction of Alcohols
Problem
Problem
Additional Methods for oxidizing Alcohol
Oxidation with KMnO4 and HNO3
Oxidation with CuO
Swern Oxidation
Problem
Solved Problem
Problem
Reduction of Alcohols
Problem
Cyclization and Rearangment of Alcohol
Problem
Problem
Mechanism
Problem
Problem
Problem
References:
Bruice, P. Y. Organic Chemistry, 4th Ed.
Solomons, T. W. G. And Fryhle, C. B. 2011. Organic Chemistry, 10th Ed. John Wiley and Sons, Inc.
Solomons, T. W. G. Fundamental of Organic Chemistry.
Wade, L.G. 2006. Organic Chemistry, 6th Ed. Peason Education, Inc., New Jersey.
