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.