Ethylene oxide
Ethylene oxide
Ethylene oxide
is a colorless and flammable gas with a faintly sweet odor, b.p. 10.7oC
. According to the A.U.P.A.C. system of nomenclature, an oxygen atom linked to
two of the carbon atoms in a carbon chain is denoted by the prefix epoxy in all
cases other than those in which a substance is named as a cyclic compound; thus
ethylene oxide is epoxyethane. Epoxy-compounds contain the oxiran(oxirane)
ring, and ethylene oxide is also known as oxiran (oxiraane). Oxiran compounds
are also referred to as cyclic ethers or alkene oxides.
Epoxides may,
in general, be prepared by epoxidation of alkenes with peroxy acids. Ethylene oxide
may be prepared as follows:
The mechanism
is possibly:
This is an
example of neighboring group participation.
Ethylene oxide
is manufactured by passing ethylene and air under pressure over a silver
catalyst at 200-400oC:
Ethylene oxide
undergoes molecular rearrangement on heating to form acetaldehyde:
Epoxides are
reduced by lithium aluminium hydride to alcohols, unsymmetrical epoxides giving
as main product the more highly substituted alcohol; thus (I) is the main
product:
On the other
hand, (II) is the main product if LAH-AlCl3 is used. Brown et al.
have shown that (II) is the major product (^90%) when BH3-BF3
is the reducing regent.
Epoxides are
readily reduced to the corresponding aalkenes by t-phosphines, e.g.,
They are
also oxidized by dimethyl sulphoxide to a-hydroxyketones (acyloins).
Ethylene oxide
is converted into ethylene glycol in dilute acid solution and into ethylene
halogenohydrins with concentrated halogen acid solutions. Ethylene oxide also
forms mono-ethers with alcohols in the presence of a smoall amount of acid as
catalyst. The mechanisms of these reactions in acid media probably follow the
same pattern, e.g., with dilute acid (with alcohols, replace H2O by
ROH):
Attack occurs
from the position remote from the +OH , and the product is the trans diol. Thus cannot be
demonstrated with ethylene oxide itself but has been, e.g., with
1,2-epoxycyclohexane. with concentrated halogen acid:
Ethylene oxide
also reacts with alcohols under the influence of basis catalysts. A possible
mechanism is :
Of particular
interest is the addition of hydrogen cyanide to form ethylene cyanohydrins:
The structure
of ethylene oxide is uncertain; it may contain ‘bent’ bonds.
When ethylene
oxide is heated with methanol under pressure, the monomethyl ether of glycol is
formed:
This is
known as methyl cellosolve; the corresponding ethyl ether is known as ethyl
cellosolve. Cellosolves are very useful as solvent since they contain both the
alcohol and ether functional groups (cf. polyethylene glycols)
The further
action of ethylene oxide on cellosolves produces carbitols, e.g.,
When glycol
is treated with ethylene oxide, diethylene glycol is formed:
Diethylene glycol
dimethyl ether (diglyme), b.p. 160oC is used as a solvent.
Ethylene
oxide reacts with ammonia to form a mixture of three aminoalcohols which are
usually referred to as the ethanolamines:
The ethanolamines
are widely used as emulsifying agents.
The mechanism
of these reactions is possibly:
In the
presence of excess of ethylene oxide, the reaction proceeds with the
ethanolamine now being the amino regent, etc.
The C-O
group (stretch) in epoxides absorbs in the region I 260-I 240 cm-1 (s),
and so these compounds may be readily distinguished from ethers.
The NMR
spectra of epoxy compounds show a t-value -7.2-7.6 p.p.m. for methylene protons
and 7.0 for methane protons. These ranges are sufficiently different from those
of CH2 and CH groups in other environments that epoxides may usually
be recognized in this way.
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