Chapter 7 Alcohols, phenols, and Thiols

Structure of Alcohols

Hydroxyl (-OH) functional group Oxygen is sp3 hybridized.

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Nomenclature of Alcohols
Compounds in which a hydrogen is replaced by an OH group. We distinguish three types:
Primary alcohols Secondary alcohols
R

R CH2 OH
R CH OH

Tertiary alcohols

R R C R
3

OH

Nomenclature of Alcohols
Common names are the name of alkyl group followed by the word alcohol
OH
cyclohexyl alcohol

OH

isopropyl alcohol
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Nomenclature of Alcohols
CH3CH2CH2CH2CHCH2OH C CH2CH2CH3 C

CH 3 CH 2 CH 2 CH 2 CHCH 2 O H CH 2 CH 2 CH 3
1 2 3

Notice that numbering starts C at alcohol group

2-propyl-1-hexanol
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More Examples
2 3 4 5 1 6

OH

HO
2 3 1

Br
5 4

H3C

CH3

2,3-dimethyl-1-cyclohexanol
2,3-dimethyl-cyclohexanol

3-bromo-2-pentanol

H3C

2 3 4 5 1 6

OH
3 4

2 1

OH

CH3
3-ethyl-5-methyl-1-cyclohexanol

H3C
4-methyl-cyclopent-2-en-1-ol
4-methyl-cyclopent-2-enol
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3-ethyl-5-methyl-cyclohexanol

Naming Priority
Acids Esters Aldehydes Ketones Alcohols Amines Alkenes Alkynes Alkanes Ethers Halides

Hydroxy Substituent
When -OH is part of a higher priority class of compound, it is named as hydroxy. Example:

OH HO O

4-hydroxybutanoic acid

Nomenclature of Phenols
OH group is assumed to be on carbon 1. For common names of disubstituted phenols, use ortho- for 1,2; meta- for 1,3; and para- for 1,4. OH is named as hydroxy. OH

OH

Cl
meta-chlorophenol 3-chlorophenol

CHO 4-hydroxybenzaldehyde
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Hydrogen Bonding in Alcohols and Phenols

H C Cl chloroethane MW 65 bp 12.3 CH3 H

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Hydrogen Bonding in Alcohols and Phenols

Unusually high boiling points due to hydrogen bonding between molecules. A positively polarized OH hydrogen atom from one molecule is attracted to a lone pair of electrons on a negatively polarized oxygen atom of another molecule This produces a force that holds the two molecules together These intermolecular attractions are present in solution but not in the gas phase, thus elevating the boiling point of the solution

R O H H

R O H

R O H

R O H

R O H

R O
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Small alcohols are miscible in water, but solubility decreases as the size of the alkyl group increases.
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Acidity and Basicity Reviewed

BrnstedLowry Acid donates a proton Base accepts a proton

Strong reacts to give weak The weaker the base, the stronger is its conjugate acid Stable bases are weak bases
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An Acid/Base Equilibrium
H2O + HA H3O+ + A-

[H3O+][A-] Ka = [H2O][HA] pKa = -log Ka

Ka: The acid dissociation constant The stronger the acid, the smaller is its pKa
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The Most Common Organic Acids Are Carboxylic Acids

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Lewis Acids and Bases

Lewis acid: accepting pair of electrons (AlCl3, BH3 and Mn+, like Zn2+, Mg2+, Na+, R3C+) Lewis base: donating pair of electrons ( H-, -OR, -NH2, R3C-, XH2O, NR3,

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The Acidity of Alcohols and Phenols

Alchols and Phenols are Weak Brnsted Acids Can transfer a proton to water to a very small extent Produces H3O+ and an alkoxide ion, RO, or a phenoxide ion, ArO

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pKa Values for Typical OH Compounds

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Relative Acidities of Alcohols

Simple alcohols are about as acidic as water. Alkyl groups make an alcohol a weaker acid. Electron-withdrawing groups make an alcohol a stronger acid by stabilizing the conjugate base (alkoxide)

Inductive Effects
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Generating Alkoxides from Alcohols

Alcohols are weak acids requires a strong base to form an alkoxide such as NaH, or metal (K, Na) Alkoxides are bases used as reagents in organic chemistry

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Phenol Acidity
Phenols (pKa ~10) are much more acidic than alcohols (pKa ~ 16) due to resonance stabilization of the phenoxide ion Phenols react with NaOH solutions (but alcohols do not), forming soluble salts that are soluble in dilute aqueous

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Substituted Phenols
Can be more or less acidic than phenol itself An electron-withdrawing substituent makes a phenol more acidic by delocalizing the negative charge Phenols with an electron-donating substituent are less acidic because these substituents concentrate the charge

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Nitro-Phenols
Phenols with nitro groups at the ortho and para positions are much stronger acids The pKa of 2,4,6-trinitrophenol is 0.6, a very strong acid

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The Basicity of Alcohols and Phenols

Alcohols are weak Brnsted bases Protonated by strong acids to yield oxonium ions, ROH2+

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Dehydration of Alcohols to Alkene

Dehydration (elimination) of water is commonly obtained using sulfuric acid (H2SO4) as a catalyst.
H3C OH CH3
H2SO4

H3CHC CHCH3 + H2O

The acid is mandatory to convert the poor leaving group OH into a good leaving group H2O.
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Dehydration
First step is protonation of the hydroxyl group.
H H3C OH CH3
H2SO4

H3C

O H CH3

Loss of water leads to a carbocation.

H H3C O H - H2O CH3 H3C CH3
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Dehydration
Second, a base removes a proton to the carbocation center.
H 3C

H3CHC CHCH3 CH3 + H2SO4

H H OSO3H

Notice that this reaction is an E1 reaction.

Rate-determining step is the formation of the carbocation.
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Dehydration
In case we have a choice between several hydrogens, the most stable alkene usually predominates
CH3 CH3CHCH2CH3 OH H3C H3PO4 H3C CH3 H2C CH + H3C 84 %

CH2 CH3

16 %

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Dehydration
As a result of the E1 mechanism, the ease of dehydration follows the order:
R R R OH R H OH R

>

>

R H

OH

That directly reflects the stability of the intermediate carbocations.

R R R R H

>

H R

>

R H
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Dehydration
Primary alcohols undergo dehydration by an E2 pathway. First, however, we generate the good leaving group.
OH H
+

H O H

The subsequent steps, removal of water and deprotonation, take place simultaneously.
OSO3H H H3C H O H H3C CH CH2
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The Reaction of Alcohols with Hydrogen Halides

HCl OH

1-propanol

Cl + H2O
1-chloropropane

HI HO
cyclohexanol

+ H 2O
iodocyclohexane

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Primary, secondary, and tertiary alcohols all undergo nucleophilic substitution reactions with HI, HBr, and HCl

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Secondary and tertiary alcohols undergo SN1 reactions with hydrogen halides

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Primary alcohols undergo SN2 reactions with hydrogen halides

ZnCl2 can be used to catalyze certain SN2 reactions

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Other Ways to Prepare Alkyl Halides from Alcohols

Using thionyl chloride (SOCl2) and Phosphorous halide (PX3)

3 alcohols are converted by HCl or HBr at low temperature SOCl2 and PBr3 are used mainly for 1 and 2 alcohols since their reactions with HX are slow.

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A Comparison of Alcohols and Phenols

OH HCl H O H

OH HCl H O H

ClCl
a phenyl cation very unstable can not formed
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Oxidation of Alcohols
Can be accomplished by inorganic reagents, such as KMnO4, CrO3, and Na2Cr2O7 or by more selective, expensive reagents

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Oxidation of Primary Alcohols

To aldehyde: pyridinium chlorochromate (PCC, C5H6NCrO3Cl) in dichloromethane Other reagents produce carboxylic acids

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Oxidation of Secondary Alcohols

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7.14 Reactions of Phenols

The hydroxyl group is a strongly activating, making phenols substrates for electrophilic halogenation, nitration, sulfonation, and Friedel Crafts reactions Reaction of a phenol with strong oxidizing agents yields a quinone
KMnO4 Or K2Cr2O7

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7.17 Thiols, Sulfur Analogs of Alcohols and Phenols

Thiols (RSH), are sulfur analogs of alcohols
Named with the suffix thiol (stronger acid than alcohol due to the size of

sulfur S larger than O )

SH group is called mercaptan

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Thiols: Formation and Reaction

From alkyl halides by displacement with a sulfur nucleophile such as SH
The alkylthiol product can undergo further reaction with the alkyl halide to give a symmetrical sulfide, giving a poorer yield of the thiol

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Sulfides
Thiolates (RS) are formed by the reaction of a thiol with a base Thiolates react with primary or secondary alkyl halide to give sulfides (RSR) Thiolates are excellent nucleophiles and react with many electrophiles

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Oxidation of Thiols to Disulfides

Reaction of an alkyl thiol (RSH) with bromine or iodine gives a disulfide (RSSR) The thiol is oxidized in the process and the halogen is reduced

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