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Chapter 9 Alcohols, Ethers and phenols. 9.1 IUPAC Nomenclature of Alcohols, Ethers and Phenols 9.1.1 Naming Alcohols 9.1.2 Naming Phenols 9.1.3 Naming Ethers 9.2 Preparation of alcohols,Ethers and Phenols 9.2.1 Preparation of alcohols

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slide1

Chapter 9

Alcohols, Ethers and phenols

9.1 IUPAC Nomenclature of Alcohols,

Ethers and Phenols

9.1.1 Naming Alcohols

9.1.2 Naming Phenols

9.1.3 Naming Ethers

9.2 Preparation of alcohols,Ethers and

Phenols

9.2.1 Preparation of alcohols

A. Preparation of alcohols by

reduction of carbonyl compounds

(1) Hydrogenation of aldehydes and

ketones by catalysis of metals

(2) Reduction of carbonyl compounds

by metal hydrides

B. Preparation of diols

slide2

9.2.2Preparation of Ethers

A. Ethers by intermolecular dehydration

of alcohols

B. Williamson Synthesis of Ethers

9.2.3 Preparation of phenols

A. Laboratory synthesis

B. Industrial synthesis

9.3 Reactions of Alcohols

The sites of reactions of a Alcohol

9.3.1 Acidity and Basicity of Alcohols

9.3.2 Conversion of alcohols to ethers

9.3.3 Oxidation of alcohols

A. Oxidation of primary alcohols

B. Oxidation of secondary alcohols

C. Oxidation of vicinal diols

slide3

9.4 Reactions of phenols

9.4.1 Acidity of Phenols

9.4.2 Electrophilic aromatic substitutions

9.4.3 Acylation of phenols

Fries rearrangement

9.4.4 Kolbe-Schmitt reaction

9.4.5 Preparation of aryl ethers

9.4.6 Cleavage of aryl ethers by hydrogen

halides

9.4.7 Claisen rearrangement of

allyl aryl ethers

9.4.8 Oxidation of phenols: Quinones

slide4

9.5 Reactions of Ethers

9.5.1 Acid-catalyzed cleavage of ethers

9.5.2 Preparation of epoxides

A.Epoxidation of alkenes by reaction

with peroxy acids

B. Conversion of vicinal halodrins

to epoxides

9.5.3 Reactions of Epoxides

A. Base-catalyzed ring opening

B. Acid-catalyzed ring opening

slide5

Acetyl halides

酰卤

Esters

Carboxylic acid

anhydrides

酸酐

Amides

酰胺

Y

Compounds with O-containing

functional groups

Alcohol Ether Phenol Aldehyde Ketone

醇 醚 酚 醛 酮

Alcohol Ether Phenol Aldehyde Ketone

醇 醚 酚 醛 酮

Carboxylic Carboxylic acid

acid derivatives

羧酸 羧酸衍生物

The interplay of these

compounds is fundamental

to organic chemistry and biochemistry

slide6

Class of Alcohols:

Primary

alcohols

Secondary

alcohols

Tertiary

alcohols

Compounds that have hydroxyl

group bonded to a saturated,

sp3-C atom-Alcohols.

Compounds that have hydroxyl

group bonded to a aromatic

ring-Phenols.

Compounds that have a oxygen

atom bonded to two carbon atom

-Ethers

Class of Ethers:

Ethers

Epoxides

slide7

Suffix:

e

ol

9.1 IUPAC Nomenclature of Alcohols,

Ethers and Phenols

P252,8.1

9.1.1 Naming Alcohols

Common name:

Alkyl + alcohol

Substitutive name:

  • Number: begin at the end nearer
  • the hydroxyl group.

Allyl alcohol

(烯丙醇)

tert-Butylalcohol

(叔丁醇)

Benzyl alcohol

(苄醇)

2-Propen-1-ol

(2-丙烯-1-醇)

Phenyl methanol

(苯甲醇)

2-Metyl-2-propanol

(2-甲基-2-丙醇)

slide8

BHT

5-Chloro-

2-methyl-

phenol

(2-甲基-5-氯

苯酚)

1,4-Benzenediol

Hydroquinone

(对苯二酚)

(氢醌)

1,2-Benzenediol

Catechol

(儿茶酚)

(邻苯二酚)

Ethyl glycol

(乙二醇)

1,2-Ethanediol

1,3-Benzenediol

Resorcinol

(间苯二酚)

ClCH2CH2CH2OH

3-Chloro-1-propanol

(3-氯-1-丙醇)

Glycerol(甘油)

1,2,3-Propanetriol

9.1.2 Naming Phenols

Phenol is the base name:

o-, m-, p-: substitutent

4-Methylphenol

p-Methylphenol

p-Cresol(甲酚)

slide9

Pyrogallol

(连苯三酚)

1,3,5-benzenetriol

(均苯三酚)

1-Naphthol

α- Naphthol

(1-萘酚)

2-Naphthol

β- Naphthol

(2-萘酚)

slide10

Symmetrical ethers (单醚)

Unsymmetrical

(Mixed) ethers (混醚)

9.1.3 Naming of Ethers

P253

Functional class IUPAC names

Tetrahydrofuran

(THF)

(四氢呋喃)

Diethyl ether

(乙醚)

Anisole

Methyl phenyl ether

(茴香醚)

(苯甲醚)

CH3CH2OCH3

Ethyl methyl ether

(甲乙醚)

tert-Butyl

phenyl ether

(苯叔丁基醚)

slide11

Suffix:yl

oxy

1,4-Dioxane

1,4-二氧六环

二 烷

Oxane

Substitutive IUPAC

Alkoxy (烷氧基)

1-Ethoxy-4-methylbenzene

(4-甲基-1-乙氧基苯)

2-Methoxypentane

(2-甲氧基戊烷)

Cyclic ethers:

slide12

9.2 Preparation of alcohols, Ethers and

Phenols

9.2.1 Preparation of Alcohols

Transformation of the several functional

groups to alcohols:

P258,8.4

A. Preparation of Alcohols by

Reduction of Carbonyl Compounds

slide13

p-Methoxy-

benzaldehyde

p-Methoxybenzyl

alcohol(92%)

(1) Hydrogenation of aldehydes and

ketones by Catalysis of metals

Aldehydes Primary alcohols

Ketones Secondary alcohols

slide14

Sodium borohydride

NaBH4

(硼氢化钠)

Lithium aluminum hydride

LiAlH4(LAH)

(四氢铝锂)

(2) Reduction of carbonyl compounds

by metal hydrides

P259,

8.5

Metal hydrides:

slide15

4,4-Dimethyl-

2-pentanone

4,4-Dimethyl-

2-pentanol(85%)

Butanal

Butanal

1-Butanol (87%)

1-Butanol (87%)

  • Reaction of NaBH4 with aldehydes
  • and ketones

An aqueous or

alcoholic solution

slide16

3,3-Dimethyl-2-butanone

3,3-Dimethyl-2-butanol

Cyclopropanecarboxylic

Acid (环丙基甲酸)

Cyclopropylmethanol

(环丙基甲醇)(78%)

  • Reaction of LiAlH4 with Aldehydes
  • and Ketones
  • Reaction of LiAlH4 with carboxylic acids
  • and esters
slide17

Benzyl alcohol

(苄醇)(90%)

Ethyl benzoate

(苯甲酸乙酯)

1°Alcohols

  • Selective reduction:
  • NaBH4 does not reduce C=C,
  • and -COOH, -COOR。
  • LiAlH4 does not reduce C=C,

Characteristics of reactions:

slide18

Reduced by LiAlH4

Reduced by NaBH4

Ease of reduction

Methyl 2-pentenoate 2-Penten-1-ol(91%)

slide19

1,2-Ethanediol

Ethylene glycol

1,2-乙二醇(甘醇)

1,2-Propanediol

Propylene glycol

1,2-丙二醇

NaBH4 LiAlH4

Solvents: H2O, ROH Et2O, THF

  • Solvents:

LiAlH4 reacts violently with water.

B. Preparation of diols

Vicinal diols

slide20

Alkaline

(碱性)

OsO4

Osmium tetraoxide

(四氧化锇)

tert-butyl hydroperoxide

(叔丁基氢过氧化物)

Hydroxylation

KMnO4 / OH-

(cold)

Syn-addition

slide21

9.2.2Preparation of Ethers

A. Ethers by intermolecular dehydration

of alcohols

Substrate: Primary alcohols

Acid-catalyzed

Products: symmetric ethers

P261,

8.6

B. The Williamson Synthesis of Ethers

Sodium alkoxide,

Alkyl halide and derivatives

Mixed ethers

slide22

The reaction characteristic:

  • SN2 reaction
  • 2. The best substrate is primary alkyl halide
slide23

Alexander W. Williamson

(1824-1904)

Alexander W. Williamson was Born in London, England,

and received his Ph.D. at the University of Giessen in

1846.His ability to work in laboratory was hampered

by a childhood injury that caused the loss of an arm.

From 1849,utill 1887, he was professor of Chemistry

at University College, London.

slide24

Bonding in organic compounds at that time was thought to be of either the

water type, as in alcohols, ROH, or of the radical type, as in ethers which

would be given the formula RO. But Williamson, by his ether synthesis,

showed that mixed ethers, with two different alkyl groups, could be prepared.

Ethers thus has to have the water-type formula ROR', and oxygen had the

equivalent weight of 8 but the atomic weight of 16. By this type of argument

he established and rationalised the structures of many of the families of

simple organic compounds. Thus, in 1850 he predicted the existence of acetic

anhydride, which was prepared in 1851.We still have some examples of his

early apparatus, and his copper pelicans, in which he prepared ether, are

shown at right. When you realise the scale on which these reactions were

carried out, and the fact that the pelican was heated over a charcoal brazier,

it is remarkable that we do not seem to have records of catastrophic accidents

taking place.

Later on Williamson, again with people such as Liebig, was responsible for

the introduction of much of the glassware which we are familiar with today,

except that it was usually fitted together with corks rather than ground

glass joints. Standard joints, blown in a mould, as we know them today

did not come into use until the middle of the last (20th) century.

Towards the end of his period as Head of Department, Williamson became

very much involved in College and University politics, and his research

suffered. This was the period when the other London colleges - Kings,

Birkbeck, Queen Mary, what is now Imperial College, and so on were

combined into a federal university, and presumably Williamson felt

the need to fight the University College corner.

slide25

9.2.3 Preparation of phenols

From aniline:

A. Laboratory synthesis

(80%)

B. Industrial synthesis

(1) Reaction of benzenesulfonic acid with NaOH

Toluene p-Toluenesulfonic p-methylphenol

acid (72%)

碱熔法

slide26

(2) Hydrolysis of chlorobenzene

卤苯水解

3. From cumene(枯烯)

Friedel-Crafts alkylation

Cumene hydroperxide

(氢过氧化枯烯)

slide27

Cumene is oxidized to cumene hydroperoxide

异丙苯法

9.3.Reactions of Alcohols

slide28

Nucleophilic

substitution

  • The sites of reactions of a Alcohol:

Weak

basicity

Nu:

Protona-

tion

Weak acidity

Elimination

Oxidation

slide29

Reversible protonated by strong acids

to yield oxonium ions(

离子):

9.3.1 Acidity and Basicity of Alcohols

Like water, alcohols are both weakly

basic and weakly acidic.

P256,8.3

As a weak base:

An alcohol An oxonium ion

As a weak acid:

An alcohol An Alkoxide Hydronium

ion(烷氧负离子) ion(水合离子)

Acid (base) conjugate conjugate

base acid

slide30

K > 1

Stroger

acid

+

Stroger

base

Weaker

acid

+

Weaker

base

In any proton-transfer

process:

Relative acidity:

Relative basicity:

P257, Table 8.1

slide31

P263.8.7

NaH, NaNH2

9.3.2Conversion of Alcohols to Ethers

Dehydration

slide32

1,5-Pentanediol

(1,5-戊二醇)

Oxane

( 烷)(76%)

  • Characteristics of the reaction:
  • Condensation(缩合反应)
  • 2. Only for primary alcohols
  • 3. The temperature of condensation is lower than elimination.
  • 4. SN2 mechanism
slide33

3-Fluoropropanoic acid

(3-氟丙酸) (74%)

3-Fluoro-1-propanol

(3-氟-1-丙醇)

9.3.3 Oxidation of alcohols

P 263

A. Oxidation of primary alcohols

PCC reagent is

soluble in CH2Cl2

slide34

Citronellol

(香茅醇)

Citronellal (82%)

(香茅醛)

[O]

Secondary

alcohols

ketones

PCC doesn’t attack C=C bond

B. Oxidation of secondary alcohols

Chromic acid

H2CrO4

slide35

AgIO3

Cyclohexanol

Cyclohexanone(85%)

C. Oxidation of vicinal diols

Vicinal diols react with HIO4, the

C-C bond is broken to form carbonyl

compounds

Ch.P225,(3)

AgNO3 is added to identify the vicinal diols

slide36

9.4 Reactions of phenols

The sites of reactions

Acidity

Acylation

Formation

of aryl ethers

Aromatic

Electrophilic

substitution

slide37

pKa = 18 pKa = 9.89

pKa = 4.74

pKa (25℃)

Substi-

tuents

Substi-

tuents

pKa (25℃)

o- m- p-

-H

-CH3

-Cl

-NO2

-OCH3

9.89 9.89 9.89

3.96

0.38

2,4-Dinitro

2,4,6-Trinitro

(picric acid)

(苦味酸)

10.20 10.01 10.17

8.11 8.80 9.20

7.17 8.28 7.15

9.98 9.65 10.21

9.4.1 Acidity of Phenols

P256,8.3

TABLE 1 The acidity constants of phenols

slide38

Electron - releasing group

Acidity is decreased

Electron – withdrawing

group

Acidity is increased

pka = 10

Substituted phenols:

Substuents

on the position

o- or p-

Electron delocalization in phenoxide ion:

slide39

9.4.2 Electrophilic aromatic

substitutions

P266;

Ch.P322,(2)

A hydroxyl group is a very powerful

activating substituent:

Bromination:

Sulfonation:

Rate control

Equilibrium control

slide40

9.4.3 Acylation of phenols

Acylating agents: acyl halides and

carboxylic acid anhydrides

Ch.P319(丙)

Phenolic

Esters

(酚酯)

Fries rearrangement:

Conversion of

aryl esters to

aryl ketones.

(9%)

p-hydroxylbenzopheone

(对-羟基二苯酮)(64%)

Phenol

benzoate

slide41

9.4.4 Kolbe-Schmitt reaction:

Carboxylaltion of phenols

Sodium phenoxide

CO2

Heated under pressure

Acidified

Salicylic acid

Aspirin

(阿斯匹林)

(乙酰水杨酸)

Salicylic acid

(水杨酸)(79%)

slide42

9.4.5 Preparation of aryl ethers

Williamson Method

A Phenoxide anion

A alkyl halide

Alkylation of hydroxyl oxygen a phenol

Why?

Me2SO4-methylating agent

slide43

9.4.6 Cleavage of aryl ethers by

hydrogen halides

The bond of O-R was broken!

The bond of

C-O in phenols

has partial double

bond character

slide44

9.4.7 Claisen rearrangement of

allyl aryl ethers

Intramolecular

reaction

Heating allyl aryl ether

The product is o-allylphenol

Transition state

slide45

Claisen was professor in Aachen in 1890,

Kiel in 1897 and Berlin in 1904.

Several syntheses especially condensation

reactions between aldehydes, ketones,

and esters (1881-1890) are connected with

Claisen´s name. He also carried out

research on tautomerism and

rearrangement reactions

(Umlagerungsreaktionen)

http://www.chemsoc.org/networks/enc/FECS/

Claisen.htm

19th Century

Claisen, LudwigBorn: Köln (Germany), 1851 Died: Godesberg near Bonn

(Germany), 1930

slide46

The sructures

of quinones:

Hydroquionoe

p-Benquinone

9.4.8 Oxidation of phenols: Quinones

(醌)

P266

slide48

9.5 Reactions of Ethers

P267,8.9

9.5.1 Acid-catalyzed cleavage of ethers

Mechanism of the reaction:

slide49

Syn-addition

Peroxy acids:

Peroxyacetic acide

(过氧乙酸)

Peroxybenzoic acide

(过氧苯甲酸)

9.5.2 Preparation of epoxides

A. Epoxidation of alkenes by reaction with

peroxy acids (过氧酸)

B. Conversion of vicinal halohydrins (α-卤代醇)

to epoxides

slide50

Intramolecular Williamson ether synthesis:

1. Anti-addition, 2. Inversion of configuration

slide51

9.5.3 Reactions of epoxides

A. Base-catalyzed ring opening

To the unsymmetric epoxide, in base-

catalyzed ring-opening, attack by nucleophile

occurs at less substituted carbon atom.

B. Acid-catalyzed ring opening

slide52

In the acid-catalyzed ring opening, the

nucleophile attacks primarily at the more

substituted carbon atom.

Anti-

hydroxylation

SN2 reaction

With inversion of configuration

slide53

Problems to Chapter 9

P276

8.24 (c), (d)

8.25 (b), (c)

8.28

8.31(a),(b)

8.33(a), (c), (e)

8.35(a),(d)

8.36(b), (e)

8.37(b)

8.38(b), (c)

8.40

8.41

8.43

8.46

8.48

8.51

8.53

8.54(b)

8.55