ALCOHOL AND PHENOL

DR. MOHD BAKRI BAKAR DEPARTMENT OF CHEMISTRY FACULTY OF SCIENCE UNIVERSITI TEKNOLOGI MALAYSIA C18-208 bakri@kimia.fs.utm.my

As petroleum decreases, demand for alternative fuel.

BIO-FUEL?

Source: petroleum & fermentation

Petronas Methanol Labuan The plant currently produces 660,000 tonnes of methanol per year, using some 55 million standard cubic feet of gas per day as feedstock

Phenolic resin

Structure of Alcohols

v General formula: R-OH v functional group: hydroxyl (-OH)

Classification of Alcohols
v Primary ROH: Carbon with OH is bonded to one other carbon.

v Secondary ROH: Carbon with OH is bonded to two other carbons. v Tertiary ROH: Carbon with OH is bonded to three other carbons. v Aromatic alcohol or phenol: -OH is bonded to a benzene ring.

IUPAC Nomenclature/Names
v Find the longest carbon chain containing the carbon with the -OH group. Drop the -e from the alkane name, add -ol. Number the chain, starting from the end closest to the -OH group. Number and name all substituents.

v v

CH3 CH3 CH CH2OH

OH CH3 CH CH2CH3
2-butanol

2-methyl-1-propanol

CH3 CH3 C OH CH3

Br
2-methyl-2-propanol 3-bromo-3-methylcyclohexanol

OH

CH3

Unsaturated Alcohols
v Priority goes to the hydroxyl group; assign that carbon the lowest number. v Use alkene or alkyne name.

OH CH2 CHCH2CHCH3
4-penten-2-ol (pent-4-ene-2-ol)

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

OH CH2CH2CH2COOH
4-hydroxybutanoic acid

Common Names
v Alcohol can be named as alkyl alcohol. v Useful only for small alkyl groups. v Examples:

CH3 CH3 CH CH2OH

CH3

OH CH CH2CH3

isobutyl alcohol

sec-butyl alcohol

Naming Diols
v Two numbers are needed to locate the two -OH groups. v Use -diol as suffix instead of -ol.

HO
1,6-hexanediol

OH

Glycols
v v 1, 2 diols (vicinal diols) are called glycols. Common names for glycols use the name of the alkene from which they were made.

CH2CH2 OH OH
1,2-ethanediol ethylene glycol

CH2CH2CH3 OH OH
1,2-propanediol propylene glycol

Naming Phenols
v v -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. Methyl phenols are cresols.
OH

OH H3C

Cl

3-chlorophenol meta-chlorophenol

4-methylphenol para-cresol

Physical Properties
v
v Unusually high boiling points due to hydrogen bonding between molecules. Small alcohols are miscible in water, but solubility decreases as the size of the alkyl group increases; why??? alkyl group is hydrophobic.

i) B.p. increases as the number of C atoms increases. Reason: larger surface area of alkyl group, creates more Van der Waals forces, thus requires more energy to boil off. ii) B.p. decreases as branching increases. Reason: smaller surface area, smaller van de waals forces.

Boiling Points

Intermolecular forces involved: a) hydrogen bonding b) dipole-dipole attractions In increasing order: Propane < dimethyl ether < ethanol

Solubility in Water

Solubility decreases as the size of the alkyl group increases.

Acidity of Alcohols & Phenols

v Alcohol can function as weak acids (proton donors)
CH3O H +
O H H

CH3O

+ H O H
H

v pKa range: 15.5-18.0 (pKa water = 15.7) v Not strong enough to react with weak bases (NaHCO3) v Acidity decreases as alkyl group increases. - simple alcohol= negatively charged oxygen atoms accessible for solvation - bulky group bonded to OH = ability of water molecules to solvate the alkoxides ion decreases

Formation of Alkoxide Ions v React methanol and ethanol with sodium metal

v React with base

Formation of Phenoxide Ion

v Phenol reacts with hydroxide ions to form phenoxide ions

O H + pKa = 10 OH

O + HOH pKa = 15.7

v Phenoxide ion is more stable; delocalization of the ve charge via resonance around the benzene ring make it stable; hence increase the acidity

v Phenol is 100 million times more acidic than cyclohexanol

SYNTHESIS OF ALCOHOLS

Synthesis (Review)
v Nucleophilic substitution on an alkyl halide, RX v Hydration of alkenes, (-C=C-) water in acid solution (H2O, H+) oxymercuration - demercuration hydroboration - oxidation

v Nucleophilic substitution on an alkyl halide, RX

Hydration of alkenes
Water in Acid Solution, H2O/H+

v Oxymercuration-Demercuration Markovnikov product formed Anti addition of H-OH No rearrangements v Hydroboration-Oxidation Anti-Markovnikov product formed Syn addition of H-OH

Oxymercuration - demercuration
v Reagent is mercury(II) acetate which dissociates slightly to form +Hg(OAc) in H2O. v +Hg(OAc) is the electrophile, will be attacked by the pi bond.

v The intermediate is a cyclic mercurinium ion, a three-membered ring with a positive charge. v Water approaches the mercurinium ion from the side opposite the ring (anti addition). v Water adds to the more substituted carbon to form the Markovnikov product.

Sodium borohydride (NaBH4), a reducing agent, replaces the mercury with hydrogen.

Hydroboration - Oxidation

v Borane, BH3, adds a hydrogen to the most substituted carbon in the double bond. v The alkylborane is then oxidized to the alcohol which is the anti-Mark product.

Hydroboration - Oxidation

Hydroboration Oxidation (continue)

Glycols (Review)
v Syn hydroxylation of alkenes q osmium tetroxide, hydrogen peroxide q cold, dilute, basic potassium permanganate (BAEYER TEST)- for alkene

Alcohols: Reduction of Carbonyl Group

v v v Reduction of aldehyde yields 1 alcohol. Reduction of ketone yields 2 alcohol. Reagents: a) Sodium borohydride, NaBH4 b) Lithium aluminum hydride, LiAlH4 c) Raney nickel

Sodium Borohydride (NaBH4)

v Hydride ion, H-, attacks the carbonyl carbon, forming an alkoxide ion. v Then the alkoxide ion is protonated by dilute acid. v Only reacts with carbonyl of aldehyde or ketone, not with carbonyls of esters or carboxylic acids.

O C H H

H C

O H H3O
+

H C

O H H

Lithium Aluminum Hydride (LiAlH4)

v Stronger reducing agent than sodium borohydride, but dangerous to work with. v Converts esters and acids to 1 alcohols.

O C OCH3 LAH H3O

+

H C

O H H

Comparison of Reducing Agents v LiAlH4 is stronger. v LiAlH4 reduces more stable compounds which are resistant to reduction.

Catalytic Hydrogenation
v Add H2 with Raney nickel catalyst. v Also reduces any C=C bonds.

OH NaBH4

O H2, Raney Ni

OH

Reaction with Carbonyl

v R:- attacks the partially positive carbon in the carbonyl. v The intermediate is an alkoxide ion. v Addition of water or dilute acid protonates the alkoxide to produce an alcohol.

Organometallic Reagents

v v v

Carbon is bonded to a metal (Mg or Li). Carbon is nucleophilic (partially negative). It will attack a partially positive carbon: a) C - X b) C = O v A new carbon-carbon bond forms.

Grignard Reagents
v v v v Formula R-Mg-X (reacts like R:- +MgX) Stabilized by anhydrous ether Iodides most reactive May be formed from any halide a. b. c. d. e. primary secondary tertiary vinyl aryl

Some Grignard Reagents

Br + Mg ether

MgBr

Cl CH3CHCH2CH3 + Mg ether

MgCl CH3CHCH2CH3

CH3C CH2 Br + Mg

ether

CH3C CH2 MgBr

Organolithium Reagents
v v v Formula R-Li (reacts like R:- +Li) Can be produced from alkyl, vinyl, or aryl halides, just like Grignard reagents. Ether not necessary, wide variety of solvents can be used.

Synthesis of 1 Alcohols 1
v Grignard + formaldehyde yields a primary alcohol with one additional carbon.

CH3 H3C C CH2 H

H C H MgBr

H C O H CH3

CH3 CH CH2 CH2

H C O H MgBr

CH3 CH3 CH CH2 CH2

H C O H H

HOH

Synthesis of 2 Alcohols
v Grignard + aldehyde yields a secondary alcohol.

CH3 H3C C CH2 H

H C H MgBr

H3C C O H CH3

CH3 CH CH2 CH2

CH3 C O H MgBr

CH3 CH3 CH CH2 CH2

CH3 C O H H

HOH

Synthesis of 3 Alcohols
v Grignard + ketone yields a tertiary alcohol.

CH3 H3C C CH2 H

H C H MgBr

H3C C O H3C CH3

CH3 CH CH2 CH2

CH3 C O CH3 MgBr

CH3 CH3 CH CH2 CH2

CH3 C O H CH3

HOH

PLANNING GRIGNARD SYNTHESIS

OH CH3CH2C-CH2CH3 C6H5

O CH3CH2CCH2CH3 + C6H5MgBr

C6H5 CH3CH2MgBr + O C CH2CH3

C6H5 2 CH3CH2MgBr + O C OCH3

Grignard Reactions with Acid Chlorides and Esters

v Use two moles of Grignard reagent. v The product is a tertiary alcohol with two identical alkyl groups. v Reaction with one mole of Grignard reagent produces a ketone intermediate, which reacts with the second mole of Grignard reagent.

Grignard Reagent + Ethylene Oxide

v Epoxides are unusually reactive ethers. v Product is a 1 alcohol with 2 additional carbons.

Grignard Reagent + Ethylene Oxide

O MgBr + CH2 CH2

O CH2CH2

MgBr

HOH O H CH2CH2

Reactions of Alcohols

Types of Alcohol Reactions

v Dehydration to alkene v Oxidation to aldehyde, ketone v Substitution to form alkyl halide v Reduction to alkane v Esterification v Williamson synthesis of ether

Dehydration of Alcohols
v Reversible reaction v Use concentrated sulfuric (H2SO4) or phosphoric acid (H3PO4) v Protonation of OH converts it to a good leaving group, HOH v Formed carbocation as intermediate v Protic solvent removes adjacent H+

Mechanism

Types of Alcohols
H R C OH H 1
O

R' R C OH H

R' R C OH R"

2O

3O

Increasing reaction rate of dehydration

Saytzeff Rule
In elimination reactions, the most substituted alkene which is the most stable alkene, is usually the major product.

Types of Carbocations
H R C H 1O
R' R C H R' R C R"

2O
Increasing stability

3O

R' R C R"

CH2 CH2 CHCH2

3O

Rearrangement to form more stable carbocation 1,2-Hydride Shift

CH3 CH3CHCH2OH
+

CH3 CH3CHCH2

H O H +

CH3 CH3C CH2 + H

CH3 CH3C CH2 + H

1,2-Methyl Shift
CH3H H3C C C CH3 H
+

CH3H H3C C C + CH3O H -H2O CH3 H

CH3OH

CH3H H3C C + C CH3 H3C

CH3H C C + CH3

CH3

CH3

Ring Expansion
H CH2OH H
+

CH2

O H +

CH2

+
H

CH2 H +

Keep in Mind!
Whenever a reaction leads to the formation of a carbocation (or radical), CHECK its structure for the possibility of rearrangement.

Oxidation of 2 Alcohols 2
v 2 alcohol becomes a ketone v Reagent is; sodium dichromate Na2Cr2O7/H2SO4 v Color change: orange to greenish-blue

OH CH3CHCH2CH3

Na2Cr2O7 / H2SO 4

O CH3CCH2CH3

orange

Greenish-blue

Oxidation of 1 Alcohols 1
v 1 alcohol to aldehyde to carboxylic acid v Difficult to stop at aldehyde v Use pyridinium chlorochromate (PCC) to limit the oxidation. v PCC can also be used to oxidize 2 alcohols to ketones.

OH CH3CH2CH2CH2

N H CrO3Cl

O CH3CH2CH2CH

3 Alcohols Dont Oxidize

v Cannot lose 2 Hs v Basis for chromic acid test

Other Oxidation Reagents

v Collins reagent: CrO3 in pyridine v Jones reagent: chromic acid in acetone v KMnO4 (strong oxidizer) v Nitric acid (strong oxidizer) v CuO, 300C (industrial dehydrogenation)

Reduction of Alcohols
v Dehydrate with conc. H2SO4, then add H2 v Tosylate, then reduce with LiAlH4

OH CH3CHCH3 alcohol
OH CH3CHCH3 alcohol

H2SO4

CH2

CHCH3

H2 Pt

alkene
OTs CH3CHCH3 tosylate LiAlH4

CH3CH2CH3 alkane

TsCl

CH3CH2CH3 alkane

H C O O Cl S O
N O C H O S O

C O O S O

CH3
p-toluenesulfonyl chloride TsCl, tosyl chloride

CH3

CH3 ROTs, a tosylate ester

Reaction with HBr

v -OH of alcohol is protonated v -OH2+ is good leaving group v 3 and 2 alcohols react with Br- via SN1 v 1 alcohols react via SN2

R O H

H3O

H R O H

Br

Br

1 alcohols react via SN2

3 and 2 alcohols react with Br- via SN1

Reaction with HCl

v Chloride is a weaker nucleophile than bromide. v Add ZnCl2, which bonds strongly with -OH, to promote the reaction. v The chloride product is insoluble. v Lucas test: ZnCl2 in conc. HCl v1 alcohols react slowly or not at all. v2 alcohols react in 1-5 minutes (turbid sol.) v3 alcohols react in less than 1 minute (turbid sol.)

Limitations of HX Reactions
v HI does not react v Poor yields of 1 and 2 chlorides v May get alkene instead of alkyl halide v Carbocation intermediate may rearrange.

Reactions with Phosphorus Halides

v Good yields with 1 and 2 alcohols v PCl3 for alkyl chloride (but SOCl2 better) v PBr3 for alkyl bromide v P and I2 for alkyl iodide (PI3 not stable)

Mechanism with PBr3

Reaction with Thionyl Chloride

Dehydration Reactions
v Conc. H2SO4 produces alkene v Carbocation intermediate v Saytzeff product v Bimolecular dehydration produces ether v Low temp, 140C and below, favors ether v High temp, 180C and above, favors alkene

Dehydration Mechanisms
H OH CH3CHCH3 alcohol
H2O CH2 CHCH3

H2SO4

OH CH3CHCH3
CH3CHCH3

CH3OH

H3O

CH3

OH2

CH3

O CH3 H

CH3OH

H2O

CH3OCH3
=>

Dehydration Mechanisms

Fischer Esterification
v Acid + Alcohol yields Ester + Water v Sulfuric acid is a catalyst. v Each step is reversible.

Write the product of the reaction of ethanol with

i) O CH3COH

O CH3COCH2CH3

ii)

O C6H5CCl
O C6H5COCH2CH3

Alkoxide Ions
v ROH + Na (or NaH) yields sodium alkoxide v RO- + 1 alkyl halide yields ether (Williamson ether synthesis)

Synthesis of phenols
1) Alkali fusion of sodium benzenesulfonate (1890)

SO3 , H2SO 4 ( sulfonation )

SO 3H

NaOH

350o C
(fusion) HCl

ONa+

NaCl

OH

2) Process cumene (isopropyl benzene)

CH3CH H2SO4

CH2

CH3 CH CH3 (kumena) O2

CH3 C OOH CH3

H3O+ OH
+

CH3 C CH3 O

CH3CH=CH2 + H2SO4 - CH3CHCH3

3) Hydrolysis of Chlorobenzene (DOW process)

350 C
ONa o

Cl

2 NaOH

150 atm
HCl

OH

Reactions of Phenols and Phenoxides Ions

1. Reduction by catalytic hydrogenation at 300C 2. Electrophilic Aromatic Substitution (o, p-director) (with bromin water obtain 2,4,6-tribromophenol) 3. Reaction to the hydroxyl groups a) formation of phenoxide ions b) esterification of phenol phenol + NaOH.+ acyl chloride phenol + acids/H+,heat c) formation of ether phenol + alkyl halide

Reactions of Phenols
Reduction of phenols

OH Ni + 3 H2 high temperature
Oxidations of phenols different from alcohol

OH

OH H2CrO4

Kuinon
O

Formation of salts

OH

ONa

NaOH

H2O

(insoluble in water)
OH

(its soluble salt)

Na

very reactive

Esterification reaction of phenols

O ONa
+

O O CH3C

CH3
+

Cl

NaCl

Formation of ether
ONa
+

O CH3CH2 Cl

CH2 CH3
+

NaCl

Acidity of alcohols and phenols

R OH
OH

Both alcohols and phenols contain OH group, and will therefore exhibit a certain degree of acidic properties.

OH

H2O

H3O+
pKa = 16.0

alkoxide ion

OH

H2O

O
Phenoxide ion

H3O+
pKa = 10.0

From pKa values, phenol is more acidic than alcohol. Why?. The answer lies on the degree of stability of the ions formed. Try doing delocalisation of the negative electron on the alkoxide and phenoxide ions.

negative charge on phenoxide ion can be delocalised, thus increasing its stability.

Provide the correct IUPAC names for the following alcohols:

OH CH3(CH2)3CHCH(CH3)2 OH H2C CHCHCH3 OH

OH OH

Write the structure for each of the following alcohols:

1) sec-butyl alcohol 2) 3-chloro-2-methylbutanol 3) 4,4-dimethyl-2-cyclohexen-1-ol

Hydration of 3-phenyl-1-butene in dilute H2SO4 is not good method to prepare 3phenyl-2-butanol, Because 2-phenyl-2-butanol is obtained, why?
OH H2O, H+

CH3

Hg(OAc)2 NaBH4

BH3.THF H2O2
H2, Raney Ni

NaBH4

Show how you would synthesis the following alcohols by adding an appropriate grignard reagent to formaldehyde?
a)

OH

b) OH

c)

CH2OH

Show how you would synthesise each alcohol by adding appropriate Grignard reagent to a ketone

a) 1-Methylcyclohexanol b) Ph3COH

Give the grignard reagent and carbonyl compound that can be used to prepare following alcohols:
CH3CH2CH2OH

OH

OH CH3CH2C-CH3 Ph

Write the mechanism for reaction of HBr with i) butanol ii) t-butyl alcohol

Determine the products for the following reactions:

CH3 H3C C CH3 CH2 OH

HCl

CH3 H3C C CH3 CH2 OH

PBr3

CH3 H3C C CH3 CH2 OH

SOCl2

Give reagents of following reactions:

OH O

OH

Provide the reagents for following reaction that shows a way to indirectly isomerize alcohols

OH OH

PCC

H2SO4

OH H2CrO4 PBr3

i) Na ii) CH3CH2CH2Br

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