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The Chemistry of AN ONION

AMINO ACID SULFOXIDES
S
O
1-PROPENESULFENIC ACID

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

Thiosulfinates are the primary

in an onion. These compounds
formed via enzymatic reaction
these compounds, which in turn
containing compounds.

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-

2014 COMPOUND INTEREST - WWW.COMPOUNDCHEM.COM

CH203 Lecture 38
December 10, 2014

Nucleophilic subs=tu=on
-Elimina=on

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-Elimina=on cyclic substrates

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.

-Elimina=on cyclic substrates

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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Subs=tu=on vs. Elimina=on

Nucleophilic subs=tu=on and -elimina=on pathways oUen are in

compe==on with each other. The ra=o of products will depend on which
mechanism is faster.

Subs=tu=on vs. Elimina=on

Nucleophilic subs=tu=on and b-elimina=on pathways oUen are in

compe==on with each other. The ra=o of products will depend on which
mechanism is faster.

12/9/14

Subs=tu=on vs. Elimina=on

Nucleophilic subs=tu=on and b-elimina=on pathways oUen are in

compe==on with each other. The ra=o of products will depend on which
mechanism is faster.

Subs=tu=on vs. Elimina=on

Nucleophilic subs=tu=on and b-elimina=on pathways oUen are in

compe==on with each other. The ra=o of products will depend on which
mechanism is faster.

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Subs=tu=on vs. Elimina=on examples

Variable

Proper,es

Electrophile

Primary

Nucleophile

Good nucleophile, strong base, not sterically

hindered

Solvent

Pro=c medium polarity

SN1 SN2 E1 E2
--

--
+

Subs=tu=on vs. Elimina=on examples

Variable

Proper,es

Electrophile

Ter=ary

Nucleophile

Weak base, weak nucleophile

Solvent

Polar pro=c

SN1 SN2 E1 E2
--
-
+

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Subs=tu=on vs. Elimina=on examples

Variable

Proper,es

SN1 SN2 E1 E2

Electrophile

Secondary

--

Nucleophile

Weak base, moderate nucleophile

Solvent

Polar pro=c

-
+

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Subs=tu=on vs. Elimina=on examples

Variable

Proper,es

SN1 SN2 E1 E2

Electrophile

Secondary

Nucleophile

Weak base, good nucleophile

Solvent

Polar apro=c

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Neighboring group par=cipa=on

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Neighboring group par=cipa=on

H2O
Cl

Cl

Cl

OH

slow, rate = k[alkyl halide][H2O]

H2O

S
Cl

Cl

S
Cl

OH

fast, rate = k[alkyl halide]

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.
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Neighboring group par=cipa=on

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Neighboring group par=cipa=on

Two chemotherapy drugs based on nitrogen mustards.

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Neighboring group par=cipa=on

The mustards cause cell death by chemically altering the DNA bases and
interrup=ng DNA replica=on.
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