Syntheses involving carbon monoxide

Hydroformylation is the addition of H2 and CO to olefins, forming an aldehyde. The catalysts used are Co, Rh, Ru, with Rh gradually taking over from Co as the catalyst of choice

Mechanism of hydroformylation
1. Tetracarbonylhydro cobalt forms a complex with the olefin

2. The -complex rearranges to a COsaturated -complex. This results in the formation of a C-Co bond in the alkyl tetracarbonylcobalt product.

3. Expulsion of the CO ligand results in the formation of an acyl tricarbonylcobalt complex

Conversion of aldehydes Aldehydes are the main products of hydroformylation, thus the synthetic route is called the oxo reaction, and products oxo products There is little use or value for the aldehydes produced by hydroformylation, and most are converted to other compounds, e.g. to primary amines by reductive amination:

The conversion of aldehydes to alcohols is performed over Ni catalysts

Uses of oxo alcohols

C4-C6: solvents for paints and plastics C8-C13: converted to dicarboxylic acids or acid anyhydrides and used as plasticizers, e.g. phthalate plasticizers Higher olefins: used as surfactants and in textiles

Conversion of aldehydes to carboxylic acid: either using air and metal salts, or temperatures of 1000C and pressures of up to 7 bar. Percarboxylic acid RCOOOH is formed as the intermediate

Conversion of aldehydes into aldol and condensation products. The process is base catalysed, e.g. by NaOH or basic ion exchange resins

Aldol addition followed by reduction converts butaraldehyde into 2-ethylhexanol, which is used as a softening alochol, or esterified with phthalic acid and used as a plasticizer

Reppe carbonylation of olefins

Olefins + CO + HX carboxylic acid or its derivative - The reaction is quite similar to the hydroformylation of olefins in which olefins + Co + H2 give aldehydes - HX is nucleophilic -H is a labile hydrogen atom -The catalyst used is metal carbonyls, e.g. Ni, Co, Fe, Rh, Fu, Pd

Reacting ethylene with CO and water produces propionic acid. In this case, X= OH

Koch carboxylic acid synthesis: In the Koch-Haaf reaction, mainly tertiary carboxylic acids are produced by reacting olefins and H. Mineral acids are used as the catalysts. The mechanism is different from that of Reppe process, as it proceeds initially by carbonium ion formation

1. The olefin is protonated, forming a carbenium ion which is stabilized by isomerization and rearrangement:

2. CO adds to the tertiary carbenium ion, forming an acylium cation which upon reaction with water forms a carboxylic acid

 Mixtures of isomeric branched carboxylic acids are produced, and the proportion is determined by the reaction conditions, e.g. 800C, 20100 bar and longer reaction times produce only trimethylacetic acid (pivalic acid) trimethylacetic acid may also be obtained from isobutene:

Characteristics of Koch acids

They have a neopentylstructure, which are thermally and oxidatively stable as they are sterically hindered. This property is of advantage in synthetic oils Other important Koch acid derivatives: Vinyl esters are used as co-monomers or in copolymerization

Oxidation products of ethylene

Ethylene oxide or oxirane and acetaldehyde are the simplest partial oxidation products of ethylene Ethylene oxide was formerly produced by the chlorohydrin process. The first step produces chlorohydrin which is then dehydrochlorinated with calcium hydroxide to etheylene oxide:

 Ethers are generally unreactive. However, ethylene oxide is extremely reactive as due to the ring being under strain. While the hybridization at its carbon atoms is sp3, the bond angle is approximately 120 0

Ethylene oxide by direct oxidation

This involves a gasphase reaction of ethylene with oxygen on Ag catalysts Secondary reactions: All these reactions are strongly exothermic. The heat of reaction is used to generate medium pressure steam

Mechanism:

Uses of ethylene oxide

As an insecticide, sterilizing agent (e.g. for rubber products) and fermentation inhibitor More important as an intermediate for synthesis Secondary reactions are due to the exothermic opening of the threemembered ring by a nucleophile such as water, alcohols, ammonia, amines and carboxylic acids

 Acidic catalysts such as mineral acids are used for reactions under high temperatures and pressure Protonation results in an oxonium complex which makes the carbon atoms more susceptible to nucleophilic attack

Ethylene glycol and higher ethylene glycol

Ethylene glycol is the most important secondary product of ethylene oxide. It is produced by adding water to ethylene oxide with sulphuric acid as a catalyst at atomospheric pressure at 50-700C, or without at catalyst at higher temperatures and pressures:

+ H2O
O HO H

+ 2H+ OH

Higher glycols are obtained by adding ethylene glycol to ethylene oxide. In the first step below, diethylene glycol is produced

Another route to obtain ethylene glycol is ethylene acetoxylation yielding diacetate (a diester), followed by hydrolysis of of the diacetate to yield ethylene glycol and acetic acid (note that acetic acid is regenerated)

Uses of ethylene glycol

As an antifreeze (95%) for automobile cooling systems As a diol in polyester manufacture, e.g. polyethylene terephthalate used in fibres, films, and bottles

Secondary products
Glyoxal is obtained from glycol by a gas-phase oxidation with air using Ag or Cu catalysts and small amounts of halogen compounds to prevent total oxidation. It is used for condensation and crosslinking, e.g. with starch, cellulose, cotton, casein or animal glue

 Dioxolane or 1,3dioacycyclopentane is derived by an acidcatalysed reaction between glycol and formaldehyde. It is a useful solvent

 1,4-dioxane is obtained by a cyclic dehydration of glycol or diglycol. It is used as a solvent for cellulose esters, oils and resins It can also be prepared by heating ethylene oxide in the presence of dilute sulphuric or phosphoric acid

Ethanolamines
Ethylene oxide reacts with 20-30%, exothermically, to produce three ethanolamines Ethanolamines are used to manufacture detergents and emulsifiers by reaction with fatty acids via the amino group or the hydroxyl group, or both

 Morpholine is derived by dehydrating diethanolamine using 70% sulphuric acid. It is used as a solvent, and an intermediate to synthesize optical brighteners and rubber chemicals

Ethylene glycol ethers

The reaction between ethylene oxide and alcohols produce glycol monoalkyl ethers The alcohols most used are methanol, ethanol and n-butanol Al2O3 is used as the catalyst These ethers are used as solvents for paint, emulsifiers and in brake fluids

Ehylene glycol dialkyl ethers are obtained by two steps: 1. The monomethyl ether is converted to its alcoholate by NaOH

2. The sodium alcoholate is etherified using an alkyl chloride or dimetyl sulphate

Uses of ethylene glycol dialkyl ethers

As inert, aprotic solvents for organometallic reactions, e.g. Grignard reactions and boron chemistry Solvents for plastics, resins, paints and varnishes In brake and hydraulic fluids

Acetaldehyde
The Wacker-Hoechst process subjects ethylene to oxidation, producing acetaldehye The catalyst contains PdCl2 and CuCl2. PdCl2 and ethylene form a charge-transfer complex which rearranges to a complex, which then decomposes to give the final products

 CuCl2 reoxidizes Pd0 to the divalent state The net reactions are:

Acetaldehyde from ethanol

Acetaldehyde may be obtained by catalytic dehydrogenation of ethanol using Ag or Cu catalysts In oxidative dehydrogenation, the combustion of hydrogen supplies the necessary heat of dehydrogenation

Acetaldehye by oxidation of alkanes

Aldehydes used to be obtained by C3 and C4 alkane oxidation, but this is not practiced today as it led to too many oxidation products

Acetic acid
The first carboxylic acid to be used by humans, e.g. in vinegar One of the most important aliphatic intermediates Oxidation of acetaldehyde in air or oxygen produces acetic acid Peracetic acid is the intermediate, and the oxidation takes place via a free radical mechanism

Peracetic acid formation

Peracetic acid reacts with acetaldehye producing -hydroxyethyl peracetate, which decomposes to give two molecules of acetate acid

Oxidation of alkanes and alkenes to acetic acid

-C4 to C8 hydrocarbons are used to produce acetic acid by oxidative degradation -In the Hls butane process, butane is oxidized without a catalyst at 60-80 bar and 170-2000C with air or oxygen, producing acetic acid, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, formic acid and propionic acid

Uses of acetic acid

Acetic acid esters are used in: cellulose acetate, which is used in paints, fibres and films Solvent for paint and resins Chloroacetic acid is a much used intermediate in organic synthesis Precursors for anhydrides such as ketene and acetic anhydride

Acetic anhydride and ketene

Acetic acid can form two anhydrides: Intermolecular: acetic anhydride, Ac2O Intramolecular: ketene or diketene H2C=C=O Ac2O may be obtained by oxidative dehydration of acetaldehye, by acetylation of acetic acid with ketene, or by carbonylation of dimethyl ether or methyl acetate

Acetic anhydride by oxidative dehydration of acetaldehye

Acetaldehyde is oxidized in air or oxygen in the Hoechst-Knapsack process. Mn acetate is used as the catalyst A primary acetyl radical forms from acetaldehyde by the abstraction of hydrogen, following which the radical is oxidized by Cu to give the acetyl cation which reacts with acetic acid to form acetic anhydride

The peracetic acid that is formed by addition of oxygen to the acetyl radical serves to reoxidize Cu+ to Cu2+

Ketene
The Wacker process for producing acetic anhydride proceeds as follows Acetic acid ketene acetic anhydride To obtain ketene, the reaction is stopped before ketene is converted to acetic anhydride

 The ketene produced may be reacted with acetic acid to produce acetic anhydride:

 In the Wacker process, acetic acid is thermally dissociated into ketene and water. The reaction is catalysed by triethylphosphate which is converted to phosphoric acid. Phosphoric acid is then neutralized with ammonia or pyridine, after which the gas is quickly cooled

Uses of acetic anhydride and ketene

acetic anhydride is an acetylating agent, e.g. to make cellulose acetate, acetylsalicylic acid, acetanilide Ketene may also be used as an acetylating agent Diketene is used for making intermediates for pharmaceuticals, dyes and insecticides

Aldol condensation of acetaldehyde

Acetaldehyde may be converted into a dimer, acetaldol, by aldol addition The process of IG Farben involves a tubular flow reactor, temperatures of 20-25oC and a residence time of several hours. The reaction is stopped by adding acetic acid or phosphoric acid
[cat.] 2CH3CHO CH3CH(OH)CH2CHO

Ethyl acetate
Important solvent for paints, also an extraction solvent for antibiotics and other pharmaceutical compounds Mostly produced from ethanol and acetic acid by acid-catalyzed esterification In the Tischenko reaction, it is produced from acetaldehyde:

2CH3CHO

CH3COOC2H5

Pyridines and alkylpyridines

Most industrially significant are pyridine, 2methylpyridine pyridine (picoline) and 2methyl-5-ethylpyridine (MEP) Much of pyridine is obtained from coal tar
CH3 H2C

CH3

CH3

2-picoline

methyl ethylpyridine (MEP)

 Pyridine is used as a basic organic solvent and for extraction, also in the synthesis of pharmaceutical compounds and herbicides 2-picoline is used as the starting material for 2-vinylpyridine, a co-monomer with styrene and butadiene that is used to improve the adhesion between synthetic fibres and tyres in the tyre industry

 The Nippon Steel process converts ethylene and ammonia to 2-picoline and MEP:

C2H4 + NH3
N

+
N