Reactions of

Naphthenes
 Overview

Pyrolysis

Oxidation to cyclohexanol and cyclohexanone –

liquid and gas phases

Oxidation to adipic acid

Nitration

Photonitrosation

Chlorination

Reactions of cyclohexanone - preparation of

Caprolactam and dicarboxylic acids
 Pyrolysis
Condition: 500 oC, without catalyst

Products: butadiene, ethylene, hydrogen, propylene

If cyclohexene, 500 – 600 oC, low pressure, to produce butadiene

and ethylene

Additional information: at 300 oC, atmospheric, catalyst: Pd or Pt,

to produce benzene
 Liquid Phase Oxidation

Polyvalent metal salts such as cobalt, form cyclohexanone and cyclohexanol

Secondary alkyl peroxide, decomposition of hydro-peroxide

 Gas Phase Oxidation

Precursor: methylcyclohexane

Reagents: air (1:5 v/v naphthene : air)

Catalyst: silver oxide on asbestos

Condition: 400 – 500 oC

Products: methylcyclohexanones

Hydrogen attached to the tertiary C is not preferable

 Oxidation to Adipic Acid

Precursor in the production of nylon 6

Two types: one-step and two-steps processes

One-step reaction

Condition: Liquid phase, 95 oC, 11 atm

Reagents: CH3COOH, HCl, cobalt hexahydrate

Air bubbled through the mixture

Additional information: Hoot and Kobe, oxidize N2

to produce NO2, 50 oC, 98% yield
 Oxidation to Adipic Acid
Two-step reaction
First step (to produce a mixture of cycohexanol-cyclohexanone)
Oxidation of cyclohexane at 125 – 160 oC, 4 – 18 atm
Catalyst: cobalt naphtenate
Second step (to produce adipic acid)
Reagents: 40% nitric acid solution, ammonium metavanadate, Cu
Condition: 50 – 150 oC, 4 – 18 atm.
Recrystalline, separation by centrifuge, 60 -70 % yield
 Oxidation to Adipic Acid

Two step reaction (continue)

Alternative condition: 60 – 80 oC, 1 – 4 atm

Reagents: air, 50 – 60 % nitric acid, Cu and V salts

92 – 98 % yield, complete conversion of cyclohexanol-cyclohexanone

Adipic acid may also converted to adiponitrile and hexamethylene

diamine for the production of nylon 6-6
 Nitration
Liquid phase nitration Gas phase nitration

Reagent: 35 % nitric acid Reagent: nitrogen dioxide

Condition: 120 – 125 oC, 4 – 5 atm

60 % yield

Alternatively: nitric acid, dispersion of molten salt

Condition: 400 oC

What we can do to nitro compounds?

 Photonitrosation
Photochemical reaction

Condition: -10 – 16 oC, Hg lamp 20 kW, light exposure at 600 nm or less

Product: cyclohexanone oxime hydrochloride

Preparation of nitrosyl chloride

Oxidation of ammonia to nitrogen sesquioxide (N2O3)

Treated with H2SO4 at atmospheric pressure to produce nitrosylsulphuric acid

Reacted with preheated HCl to produce NOCl

 Chlorination

Reagents: 3% benzoyl peroxide, PCl3

Condition: 25 – 40 oC, UV irradiation

73 – 74 % yield, distillation to produce a colourless oil, terpene-like

odor

Use as insecticide

Additional information: commonly chlorination being used or reacted

with benzene
 Reactions of
Cyclic Ketones
Cyclohexanone and Cyclopentanone
 Preparation of Caprolactam
Important precursor for the preparation of nylon

Use of cyclohexane – converted to cyclohexanone or nitrocyclohexane

Cyclohexanone to an oxime

Reagent: hydroxylamine hydrochloride

Beckman rearrangement to produce caprolactam

Reagent: ~60% sulfuric acid

Preparation of Caprolactam

Reduction of nitrocyclohexane to cyclohexanone oxime

Reagents: ammonium sulfide or sodium bisulfide

Alternative reagents (by Grundman):

ammonia, Raney Ni and trace of alkali

Alternative procedure:
Reagent: MeOH or EtOH with ammonia, Ni-Cr
Condition: heating under pressure
a second thought...
Preparation of Dicarboxylic Acid

Oxidation

In the presence of air and under pressure

Catalyst: manganese or cobalt salts

Condition: 200 oC, air pressure at 25 atm

Yield: cyclopentanone → glutaric acid,

methylcyclohexanone → methyladipic acid

Preparation of Dicarboxylic Acid

Reaction with carbon dioxide

Alternative route to produce dicarboxylic acid compounds
Catalyst: reduced manganese chromite, free acetic acid
Condition: aqueous cyclohexanone, 200 oC, 20 hs, under CO2
pressure
Yield: pimelic acid
 Summary
Production of naphthenes

Physical treatments – azeotropic / extraction distillation

Chemical treatments – dehydrogenation-hydrogenation, ring

closure, ring enlargement

Reactions
Pyrolysis – to produce alkene

Oxidation to cyclohexanol and cyclohexanone – liquid and gas

phases

Oxidation to adipic acid

Nitration
Photonitrosation

Chlorination

Reactions of cyclohexanone - preparation of Caprolactam and

dicarboxylic acids
 Assignment
Caprolactam is a cyclic amide of caproic acid. Beside its disadvantages to our health
(cause skin and eye irritation, toxic to digestion and inhalation systems), it is a primary
industry in textile.

Describe the chemical process in the production of nylon-6 from caprolactam

includes alternative process.

Suggest another three compounds / substances / applications of caprolactam.

Give your justification (or references) to your suggestions. It is recommended
for suggesting green chemistry. OR

Describe health and environmental issues relating to the production of

caprolactam and their derivatives. Suggest how you could counter the
problem.

At least 3 pages A4 (or around 6,000 characters or 1,000 words)

Font: either Times New Roman or Arial

Font size: 12 with 1.5 spacing

Full mark: 15 marks

Format: Soft-copy, then email to me..!