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The Chemistry of AN ONION: Amino Acid Sulfoxides
The Chemistry of AN ONION: Amino Acid Sulfoxides
O
S
O N I O N O D O U R & T H I O S U L F I N AT E S
SYN-PROPANETHIAL-S-OXIDE
As onions are sliced, they release a class of
enzymes, allinases, which break down amino
acid sulfoxides. A specific compound produced
during this process is 1-propenesulfenic acid,
which is rearranged by another enzyme, called
lachrymatory factor synthase, to produce synpropanethial-S-oxide. Production of this gas
peaks 30 seconds after mechanical damage to
the onion, and it stimulates sensory neurons in
the eye causing a stinging sensation; the eye
therefore produces tears to flush it out.
O
R'
S
R
ALLICIN
S
S
flavour and odour producing molecules
are not present in intact bulbs, but are
from sulfur amino acids. Allicin is one of
quickly breaks down to form other sulfur-
CH203
Lecture
38
December
10,
2014
Nucleophilic
subs=tu=on
-Elimina=on
12/9/14
In
the
more
stable
chair
conformer
of
this
cis
cyclohexane
deriva=ve,
the
chloride
is
axial.
There
are
two
hydrogens
which
are
trans
and
axial
to
the
chloride
and
thus
also
an=
coplanar.
The
alkene
might
be
formed
by
elimina=on
to
give
two
dierent
alkenes.
The
more
subs=tuted
alkene
is
observed
as
the
major
(Zaitsev)
product.
In
the
trans
isomer,
the
chloride
is
axial
only
in
the
less
stable
chair
conformer
where
the
isopropyl
group
is
forced
to
be
axial
as
well.
In
this
conformer
there
is
only
one
hydrogen
which
is
trans
and
axial
to
the
chloride
and
thus
also
an=
coplanar.
The
only
alkene
which
can
be
formed
is
the
less
subs=tuted
(non-Zaitsev)
product.
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12/9/14
12/9/14
Variable
Proper,es
Electrophile
Primary
Nucleophile
Solvent
SN1
SN2
E1
E2
--
--
+
Variable
Proper,es
Electrophile
Ter=ary
Nucleophile
Solvent
Polar pro=c
SN1
SN2
E1
E2
--
-
+
10
12/9/14
Variable
Proper,es
SN1 SN2 E1 E2
Electrophile
Secondary
--
Nucleophile
Solvent
Polar pro=c
-
+
11
Variable
Proper,es
SN1 SN2 E1 E2
Electrophile
Secondary
Nucleophile
Solvent
Polar apro=c
12
12/9/14
13
Cl
Cl
OH
H2O
S
Cl
Cl
S
Cl
OH
The
hydrolysis
of
a
primary
alkyl
chloride
is
slow
in
water.
The
rate
is
second
order
as
expected
for
an
SN2
reac=on.
The
hydrolysis
of
a
sulfur
mustard
is
more
rapid.
The
rate
is
rst
order
in
the
mustard
only.
14
12/9/14
15
16
12/9/14
The
mustards
cause
cell
death
by
chemically
altering
the
DNA
bases
and
interrup=ng
DNA
replica=on.
17
18