Topic 4

Major Bulk Organic

Chemicals from Benzene
 Bulk Organic Chemicals from Benzene

Benzene → Phenol → Bisphenol A

→ Cyclohexanone
→ Alkylphenol
→ Chloronated phenol

→ Chlorinated benzen
→ Cyclohexane → Cyclohexanone
↓
Adipic acid
Caprolactam

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 Synthesis of Phenol (Carbolic acid) (I)

• Both the sulfonation and chlorination reactions are electrophilic aromatic

substitution on an aromatic ring.

• Sulfonation of benzene followed by desulfonation with caustic.

• These routes are no longer used commercially.

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 Synthesis of Phenol (Carbolic acid) (II)

• A minor route (2% of phenol production) is using surplus of toluene from

petroleum refining.

• Oxidation with a number of reagents gives benzoic acid. Further oxidation to

hydroxybenzoic acid and decarboxylation yields phenol.

decarboxylation

Toluene

hydroxybenzoic acid
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 Synthesis of Phenol (Carbolic acid) (III)

• Approximately 95% of the cumene is used to make phenol and acetone.

• The main route involves a fascinating rearrangement of cumene hydroperoxide

where a phenyl group migrates from carbon to an electron deficient oxygen atom.

• Concentration of the hydroperoxide to 80 % is followed by the acid-catalyzed

rearrangement at 70-8O °C. The overall yield is 90-92 %.

Isopropylbenzene or
1-(methylethyl)benzene 5
 Synthesis of Bisphenol A

• Bisphenol A is manufactured by a reaction between phenol and acetone, the two

products from the cumene hydroperoxide rearrangement.

• The temperature of the reaction is maintained at 50°C for about 8-12 hr.

• A slurry of BPA is formed, which is neutralized and distilled to remove excess

phenol.

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 Synthesis of Bisphenol A

• The mechanism of this reaction using the following stepwise information

- (1) protonation of the carbonyl;
- (2) electrophilic attack on the aromatic ring;
- (3) rearomatization by proton loss;
- (4) another protonation, but then loss of a water molecule; and
- (5) electrophilic attack and rearomatization.

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Synthesis of Bisphenol A

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 Application of Bisphenol A
• The major uses of BPA are in the production of polycarbonate resins (63%) and
epoxy resins (27%).

• Polycarbonates (PC) have major outlets in automotive parts, compact discs,

eyeglasses, and sheet and glazing applications.

• Polycarbonate (PC) grade bisphenol A is > 99 % p, p’ isomer.

• The epoxy grade is 95% p, p’ isomer (together with 5% o,p’ isomers).

• o,p isomers can be separated by a combination of distillation and crystallization.

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99% PC grade

Made of Polycarbonate

95% epoxy grade

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 Alkylphenols
• When phenol was alkylated with propylene trimer by a Friedel–Crafts reaction ,
nonylphenol (alkylphenols) was produced.

• When nonylphenol reacted with ethylene oxide, an ethoxylate was produced.

• This is an important surfactant for industrial detergents and has also been used
in liquid dishwashing detergents. It has low-foam properties and good
detergency.
Formation of electrophile

H2C CH H2C CH H2C CH Al - Cl 3

CH3 CH3 CH3

Propylene

Electrophilic substitution

+ -
CH2 CH CH2 CH CH2 CH Al-Cl 3

CH3 CH3 CH3

OH
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 -
H H 2C CH CH 2 CH CH 2 CH Al-Cl 3

CH 3 CH 3 CH 3

+
-H
OH

CH 2 CH CH 2 CH CH 2 CH 2

CH 3 CH 3 CH 3

Nonyl phenol

O H
O
Epoxide
H2C CH 2

CH 2 CH CH 2 CH CH 2 CH 2

CH 3 CH 3 CH 3

Nonyphenol Ethoxylate
Anionic surfactant
O CH 2 CH 2 OH 12
 Chlorinated phenol
• The most important chlorinated phenol is 2,4-dichlorophenol, the raw material for
herbicide, 2,4-dichlorophenoxyacetic acid or 2,4-D. (weed killers, are pesticides
used to kill unwanted plants)

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 Chlorinated phenol

• Pentachlorophenol, made by exhaustive chlorination of phenol, is a wood

preservative and slimicide. (a chemical that prevents the growth of slime in
paper stock)

• The chlorine atoms make it highly lipophilic and, when it enters the body via the
food chain, it accumulates in fatty tissue.

• The same is not true of 2,4-D, whose carboxyl group may facilitate its excretion.

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 Chlorinated benzenes

• Chlorobenzene results from the liquid-phase chlorination of benzene at

slightly above room temperature with a ferric chloride catalyst.

• Chlorobenzene condenses with trichloroacetaldehyde (chloral) to yield the

insecticide 1,1,1-trichloro-2,2-bis- ( p-chlorophenyl)ethane (DDT).

Dichlorodiphenyltrichloroethane 15
 Chlorinated benzenes
DDT
• known to be very persistent in the environment,
• will accumulate in fatty tissues, and
• can travel long distances in the upper atmosphere.

• DDT was remarkably effective in mosquito control

• A worldwide ban on its agricultural use but its limited use in disease vector
control continues because of its initial effectiveness in reducing deaths due to
malaria

• It can be used as an indoor pesticide in regions where malaria is a major problem.

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 Cyclohexane

• Benzene can be quantitatively transformed into cyclohexane by hydrogenation over

either a nickel or platinum catalyst.

• This reaction is carried out at 210 0C and 350-500 psi, sometimes in several reactors
placed in series. The yield is over 99%.

• Although some cyclohexane is used as a solvent, its major market is for the
production of adipic acid and caprolactam.

hydrogenation

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 Cyclohexanone

• Air oxidation of cyclohexane with a cobalt or manganese (II) naphthenate or

acetate catalyst gives a mixture of cyclohexanone and cyclohexanol.

oxidation with
Air oxidation
50% nitric acid
125-160 0C
50-250 psi

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 Adipic acid (1,6 – hexandioic acid)

The cyclohexanone/cyclohexanol mixture (sometimes referred to as ketone-

alcohol, KA mixture, or "mixed oil") is further oxidized with 50% nitric acid with
ammonium vanadate and copper present as catalysts at 50-90 °C and 15-60
psi for 10-30 min. The further oxidation to adipic acid is very complex but occurs in
good yield, 94%

For nylon 6,6

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 Caprolactam
• Some of the cyclohexanol in cyclohexanone/cyclohexanol mixtures can be
converted to cyclohexanone by a ZnO catalyst at 400 0C.

• Then the cyclohexanone is converted into the oxime with hydroxylamine.

• The oxime undergoes a very famous acid-catalyzed reaction called the

Beckmann rearrangement to give caprolactam.

• Sulfuric acid at 100-1200C or phosphoric acid is also used after treatment with
ammonia, the by-product becomes ammonium phosphate, which can be sold as
a fertilizer.

• The caprolactam can be extracted and vacuum distilled, bp 1390C. Overall yield is
90%. Oxime Caprolactam

Hydroxyl
amine 20
 Caprolactam

Formation of oxime

• Nucleophilic addition to a ketone followed by subsequent dehydration.

• Oximes are common derivatives of aldehydes and ketones because they are solids
that are easily purified.

Hydroxyl amine

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 Caprolactam
• Acid catalyzed Beckman rearrangement (a rearrangement to electron-deficient
nitrogen).
• Protonation of the hydroxyl followed by loss of a water molecule forms the positive
nitrogen, but the R group can migrate while the water leaves, so the nitrenium ion
may not be a discreet intermediate. Attack of water on the rearranged ion and a
proton shift to form the amide completes the process.

rearranged ion

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 Caprolactam

• All of the caprolactam goes into nylon 6 manufacture, especially fibers (80%) and
plastic resin and film (20%).

• Nylon 6 is growing rapidly, especially in certain markets such as nylon carpets.

• Nylon 6 is made directly from caprolactam by heating with a catalytic amount

of Water.

• Nylon 6 is only made from one kind of monomer, a monomer called caprolactam.
Nylon 6 is polycaprolactam (IUPAC: poly(hexano-6-lactam)).

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