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Organic Chemistry
CHNG 10 ALCOHOLS & PHENOLS

Mendeleev

Hamilton

Hartree

GII THIEU CHNG

10.1. RU 10.1.1.DANH PHAP & ONG PHAN 10.1.2.CAC PHNG PHAP IEU CHE 10.1.3. TNH CHAT 10.1.4.NG DUNG
10.2. PHENOL 10.2.1. DANH PHAP & ONG PHAN 10.2.2. CAC PHNG PHAP IEU CHE 10.2.3. TNH CHAT 10.2.4. NG DUNG

DANH PHAP

DANH PHAP

OH

OH

CH3CHCH2CHCH(CH3)2
5-methyl-2,4-hexanediol

OH CH2CH2C(CH3)2

2-methyl-4-phenyl-2-butanol

OH

4,4-Dimethylcyclohexanol

H3C

CH3

H
trans-2-Bromocyclopentanol

Br

HO

LIEN KET TRONG RU

Alcohols
Bond O-H (free) O-H (H b ond ed) C-O Frequency, cm 3600-3650 3200 - 3500 1000 - 1250
-1

Inten sity Weak Medium, broad Medium

IR spectrum of 1-hexanol (Fig 12.8)

Example: Mass Spectrum of Methanol (CH3OH)

m/z 12 13 14 15 16 17 28 29 30 31 32 33 34 Rel. Abundance 0.72 2.4 13. 0.21 1.0 6.3 64 3.8 100. 66. 0.98 0.14
Rel. Abundance, %

0.33

100 90 80 70 60 50 40 30 20 10 0

31

15

10

13

16

19

22

25

28

31

34

37

m/z

CH3OH + e- CH3OH+ + 2eCH3OH + CH2OH+ + H CH3OH + CH3+ + OH CH2OH + H2 + CHO+

40

Chemical Properties

Alcohols as acids Sterically hindered alcohols such as tert-butyl alcohol are less acidic (have higher pKa values) stronger acids than terminal alkynes and primary or secondary amines Alkoxides prepared by the reaction of an alcohol with sodium or potassium metal

Hydrogen Bonding
150
H2 O HF H2Te

Boiling Point (OC ),

100 50 0 -50 -100 -150 -200 1 2

SiH4 CH4

Water
H2S H2Se SnH4

NH3

HF Ammonia Methane

GeH4

extrapolation
6

3 Period

1. Water, HF, and NH3 show unusually high bp. 2. Dotted lines depict bp if there were no H-bonding. 3. All others follow normal trend.

Hydrogen Bonding in Water

H + -O H H
Hydrogen bond, intermolecular, 4 - 25 kJ/mol
+

H
-+

O H

--

H H
-+

Chemical Bond, intramolecular, 150 - 600 kJ/mol

H + H O --

O H

Hydrogen Bonding in Alcohol

R + O H H
+

R
-

O H

R H
+

R O H

O R

Hydrogen Bonding and Boiling Point

Compound Water Methanol Ethanol Propanol bp ( C) 100 65 78 97
o

Acidity & Basicity

Like water, alcohol can act as an acid or as a base.
H
R O H

H Cl

O+ H

Cl

base
Ar O H

acid

oxonium ion
H

H Cl
Ar

O+ H

Cl

RO

+
H

alkoxide ion

O+ H

acid

base
phenoxide ion
O

+
H

H O+ H

Conversion to Alkyl Halides

Hydroxyl groups are poor leaving groups Reaction of Alcohols with HX

Tertiary alcohols: SN1

O H H-Cl H3O+
+ H O H

Step 1

H O+ H

Cl-

Step 2 H O+ H

Step 3 Cl+ Cl

Conversion to Alkyl Halides

Conversion to Alkyl Halides

Conversion to Alkyl Halides

Conversion to Alkyl Halides

Primary Alcohols: SN2

Step 1 H H Step 2 ClH H O H H O+ H H-Cl H3O+ H H H O+ H Cl-

Cl

Use of Lewis acids

Step 1 H H Step 2 ClH H O H ZnCl2 O+ H ZnCl2 H H -

H H

H O H

ZnCl2 O+ ClH ZnCl2 O H

Cl

H H

Conversion to Alkyl Halides

Conversion to Alkyl Halides

Reaction of Alcohols with PBr3

Br P Br PBr3 R Br P Br O+ BrH
H O P Br Br

Step 1

R O H

Br

Step 2 Br-

H O+ P Br Br

R Br

Conversion to Alkyl Halides

Conversion to Alkyl Halides

Reaction of Alcohols with SOCl2

Cl Cl S O SOCl2 Cl O Cl S O O+ H ClO Cl S O HCl

Step 1

O H

S Cl O+ H

Step 2

Cl S O O ClCl SO2

Leaving Groups

Tosylates (Ts), Mesylates (Ms), and Triflates (Tf): Leaving Group Derivatives of Alcohols
O -O S O O -O S O H H H O -O S O F F F

OO R R HH

O O Cl S S Cl O O
Base H +O R O S O
R

H O +O R S Cl O-

O S O

Sulfonates as Leaving Groups

Recall: SN2 inversion of configuration

R O O S O NuNu R R2 R3 R1

R1

R2 R3

Triflate anion is such a good leaving group that even vinyl triflates can undergo SN1 reaction
O O S O

F F F

-O

O S O

F F F

Synthesis of Ethers

Intermolecular Dehydration of Alcohol

This reaction occurs at lower temperature than the competing dehydration to an alkene does not generally work with secondary or tertiary alcohols (elimination competes strongly)

H OH
H OH

H2SO4 H2O 180oC

H2SO4 O 140oC

Synthesis of Ethers

Mechanism
Step 1 H O H
Step 2

H+

H O H + H

O H O H + H O

Williamson Ether Synthesis

Synthesis of unsymmetrical ethers

Recall: the alkyl halide (or alkyl sulfonate) should be primary to avoid E2 reaction, Substitution is favored over elimination at lower temperatures
Step 1 H O H
Step 2

NaH

O I

AlkoxymercurationDemercuration

Markovnikov selectivity
H H H Hg(OAc)2, ROH R O H H H Hg(OAc) R O H H H H

R O H

H H Hg(OAc)

NaBH4, OH-

Reaction of Ethers

Acyclic ethers are generally unreactive, except for cleavage by very strong acids
Step 1 HBr O
Step 2 Br+O H Br H O

+O H

Br-

Step 3 HBr O H +O H H BrBr

Alcohol Protecting Groups

The protecting groups are used to protect primary alcohols from reacting

Added before the reaction and removed after

Base

Alcohol Protecting Groups

Silyl Ethers

Tert-butyldimethylsilyl (TBDMS) Base = pyridine, imidazole

Base H

Si Cl

+O R

Si

Si

Removal: fluoride ion

Bu4N+ FR O Si then H2O R OH

Protection of Alcohol

It often happens, particularly during synthesis of complex molecules, that one functional group in a molecule interferes with an intended reaction on a second functional group elsewhere in the same molecule. - p 682.
Mg CH3CH2CH2Br ether
Mg HOCH2CH2CH2Br ether

CH3CH2CH2MgBr

HOCH2CH2CH2MgBr

Trimethylsilyl (TMS) ether

Chlorotrimethylsilane
Triethylamine

TMS ether

ROH

H3C

Si

CH3 (CH3CH2)3N

H3C

Cl CH 3

R O CH3

Si

CH3

(CH3CH2)3NH-Cl

ROH is now blocked or protected!!!

H3C

R O CH3

Si

CH3

H3O+ R O

Si H O CH3

H3C

CH3

Step 1: Adding Protection Group

(CH3)3SiCl

HOCH2CH2CH2Br

(CH3CH2)3N

(CH3)3SiOCH2CH2CH2Br

Step 2a: Carrying Out Reaction

(CH3)3SiOCH2CH2CH2Br

Mg ether

(CH3)3SiOCH2CH2CH2MgBr

Step 2b: Carrying Out Reaction

O (CH3)3SiOCH2CH2CH2MgBr

OH H3O+ (CH3)3SiOCH2CH2CH2CHCH3

CH3CH

Step 3: Removing Protection Group

OH (CH3)3SiOCH2CH2CH2CHCH3 H3O+

OH HOCH2CH2CH2CHCH3

(CH3)3SiOH

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