POST LAB DISCUSSION FOR SPECIAL SYNTHESIS

As a disclaimer, the synthetic procedure performed for the special synthesis deviated
somewhat from the supposed procedure, this is because the starting material, cyclohexanol (a
secondary alcohol) was not available. The substitute alcohol for this exercise is the primary
alcohol, isoamyl alcohol. Due to this, the overall reaction was revised as well as the reaction
mechanism and is shown below:
(insert overall reaction and reaction mechanism here)
As seen from the figure above, the isoamyl alcohol being a primary alcohol was oxidized first by
potassium permanganate to the aldehyde, 3-methylbutanal, before undergoing acid-catalyzed
oxidation using nitric acid to form the carboxylic acid, 3-methylbutanoic acid (also known as
isovaleric acid).
The synthesis proper was inititated by mixing around 9.3mL of isoamyl alcohol and 22.9
grams of potassium permanganate with 125mL of distilled water and 1mL of sodium hydroxide
and was allowed to stand for 15 minutes. Since the reaction is exothermic, an increase in
temperature was observed in the reaction mixture (appeared as a purplish brown mixture). The
reaction mixture was placed n an ice bath for 20-25 minutes and was heated near boiling in a
hot plate. A spot test should have been performed to determine if there is excess potassium
permanganate but is futile since there is no sodium bisulfite to react with the excess oxidizing
agent (potassium permanganate). Due to this, there is a high possibility that most if not all of the
isoamyl alcohol was immediately oxidized to form the carboxylic acid product. Most of the error
in the exercise could be attributed to the steam distillation that followed. The mixture was steam
distilled for around 2 hours at first but since this took some time and the necessary distillate is
around 80mL, the mixture was distilled via simple distillation (without thermometer).
Unfortunately due to this, the mixture shoot up and some of the supposed pot residue was
added to the distillate (the distillate appeared gray instead of colorless). The distillate then
undergoes series of liquid-liquid extraction which involved solid sodium chloride (salting out
agent) and dichloromethane, 10% sodium hydroxide, and saturated sodium chloride solution. In
all of the liquid-liquid extraction performed, the aqueous layer was discarded and placed in
halogenated waste while the organic layer was kept and dried using sodium sulfate. To isolate
the aldehyde intermediate as well as to determine its yield, the dried organic layer was distilled
wherein the pot residue was obtained (appeared as yellow liquid). The pot residue was found to
have a mass of 0.878 grams. With respect to the theoretical yield of______, the computed
percent yield is________. The obtained aldehyde was used for the subsequent oxidation using
nitric acid. Due to the relatively low yield, around 1mL of the aldehyde was added dropwise to
the nitric acid in an Erlenmeyer Flask while maintaining the reaction temperature around 55 to
60 degrees (NOTE: The reaction vessel is shaken after each dropwise addition and was only
performed in the fumehood). After dropwise addition for 30 minutes, the reaction mixture was
gradually heated to around 100 degrees Celsius in the succeeding 15 minutes. The reaction
mixture was then allowed to cool at room temperature. An error was again committed in this
portion of the synthetic procedure which is the isolation of the product. Since the supposed
product (adipic acid from cyclohexanone) for the special synthesis is a solid, cooling in ice bath
and subsequent suction filtration is to be employed. The procedure in the schematic diagram
unfortunately was not revised (should have been simple distillation) hence 3-methyl butanoic
acid was discarded instead of being isolated as the final product. Although even simple
distillation is employed, the amount of reactants is relatively low (6mL) in order for it to be
efficient and useful. The obtained solids for this synthetic procedure therefore is not the desired
product and could probably have been a side product and/or impurity. And for this reason, the
second portion of the synthetic procedure has no relevant data regarding percent yield. These
solids were relatively few and was not filtered thru suction and was immediately subjected to
test tube reactions which include sodium bicarbonate as well as iodoform test (see table 10.5 for
the results). The characterization test performed was somewhat inappropriate since the
iodoform test is mainly a test for methyl ketones which apparently was the anticipated
interemediate (2-pentanone was erroneously presumed to be the intermediate) which explains
the negative results for the test upon characterization. The appropriate substitute for iodoform
test is the use of Bradys reagent to confirm the identity of the aldehyde which serves as the
intermediate. The sodium bicarbonate test is appropriate since it will react with the carboxylic
acid and would have carbon dioxide as a by-product (observed as bubling) but unfortunately it
was futile since the liquid portion of the crude product should have been characterized instead
of the solid because the desired product is in liquid form.
The properties of the starting material, the intermediate, and the synthetic product based
on literature is outlined below:

Compound Melting and/or Boiling Point Appearance

mp -117.2 degrees Celsius
Isoamyl alcohol
bp760 130.5 degrees Celsius
mp -51 degrees Celsius
3-methylbutanal
bp 92-93 degrees Celsius
mp -29 degrees Celsius
3-methylbutanoic acid bp 175 to 177 degrees
Celsius
Liquid; characteristic,
disagreeable odor; pungent,
repulsive taste.
Colorless liquid; pungent apple-
like odor
Colourless liquid; strong pungent
cheesy or sweaty smell

Comparing the data in the table above with that of Table 10.2 and 10.3, the isolate intermediate
and product has somewhat different appearance than expected. Coupled with the inconclusive
data on characterization and this observations it is unfortunate to say that the objective of this
experiment was not met.