Experiment 2

Prelab questions

1. What is nucleophilic substitution?

Nucleophilic sucstitution refers to the reaction wherein a nucleophile, electron pair donor, is reacted
with an electrophile. The electrophile contains a leaving group for the reaction to occur.

2. What are the two types of nucleophilic substitution?

The two types of nucleophilic substitution are Sn1 and Sn2. In the Sn1, the carbon becomes a carbocation.
Enabling the nucleophile to attack the carbocation. In the other hand, S n2 is a backside attack making
the inversion of configuration.

3. Describe and explain the reactivity of alcohols under these conditions.

Secondary and tertiary alcohols undergo S n1 reactions with hydrogen halides while S n2 is favored in
primary alcohols. Tertiary and secondary can’t undergo Sn2 due to steric hindrance and unstable primary
carbocations can’t undergo Sn1.

4. Are there any competing reaction under specified conditions? Describe in detail.

Substitution reactions competes with elimination reactions and carbocation rearrangements.

Carbocation rearrangements are only for Sn1 reactions. Carbocation rearrangements are looking to
create the most stable carbocation. It can occur by hydride shift and alkyl shift.

Sn1 competes with E1. Therefore, Sn2 competes with E2. Elimination takes place under the similar
conditions as substitution reactions.

Postlab questions

1. What is t-butyl alcohol more reactive than isopropyl alcohol under Lucas’ conditions?
2. Draw the mechanism of the synthesis.
3. Why use conc. HCl and not dilute HCl solution?
4. What is the purpose of adding brine during the work-up?
5. Can you suggest other methods to purify the crude chloroalkane?

Experiment 3

Prelab questions

1. What is electrophilic substitution?

2. Show the general mechanism for electrophilic addition reactions.
3. What is the difference between syn and anti addition?
4. Any biological relevance of the experiment?
5. What are the products when unsaturated fatty acids react with singlet oxygen?
6. What is the difference between the stereodescriptors, threo and erythro?

Postlab questions

1. Draw the reaction scheme for in the experiment.

 2. What is the mechanism? Give the underlying scheme.
3. Give basis for the regioselectivity, chemoseelectivity and stereoselectivity of the reaction.
4. Why are sulfites used for removing excess potassium permanganate? Show the reaction.
5. What is the purpose of adding hydrochloric acid?
6. Give other examples of metal oxide oxidants in organic synthesis which go via syn addition.

Experiment 4

Prelab questions

1. What is the general principle of Markonikov’s addition?

2. Sketch a general mechanism for Markonikov’s addition.
3. What reactions involve Markonikov’s addition?
4. Provide the synthetic applications of halohydrin compounds.

Postlab questions

1. Why is NBS a more convenient reagent for carrying-out bromohydrin synthesis?

2. What other reagents can be used to carry-out bromo-hydration of alkenes?
3. Sketch and discuss the mechanism underlying the synthesis of 2-bromo-2-(4-tolyl)ethanol using
NBS.
4. Aside from water, what other nucleophilic solvents can be used to prepare other derivatives?
5. What is the purpose of washing the DCM layer with sodium hypochlorite?

Experiment 5

Prelab questions

1. Desctibe the electrophilic aromatic substitution and its mechanism.

Electrophilic aromatic substitution (SEAr) is an organic reaction in which an atom that is

attached to an aromatic system, usually hydrogen, is replaced by an electrophile.

2. What is the effect of introducing a nitro group to an aromatic compound?

The ring will have carbocation and the ring will be deprotonated by the base to transfer the
bond of hydrogen into the positively charge carbon as soon as the nitro group was bonded to an
aromatic ring.

3. What are the limitations of the nitration reaction?

 Rates relative to benzene differ from 68-80% sulfuric acid and the higher end of this range are
not completely measures of relative reactivity.

4. Any biological significance of this reaction? i.e. (nitration of nucleobases in DNA)

Nitric oxide is a stable molecule as a radical species. The smallest signal molecule is formed from
oxygen and L-arginine by enzymes. Its role is not only in physiological regulation such as platelet
aggregation, blood pressure, and neuronal function, but also in pathophysiological states.

Postlab questions

1. Why is it important to cool down sulfuric acid while nitric acid is being added?

Commercial concentrated nitric acid is 68% HNO3. The remainder is water. When concentrated
nitric acid is added to concentrated sulfuric acid, the sulfuric acid is in excess, and the bulk of the
heat generated comes from the hydrolysis of H2SO4.

2. Why are nitro compounds usually yellow in color?

UV-spectra that the nitro group causes a pronounced shift of l max to longer
wavelengths when conjugated to unsaturated p systems, a bathochromic shift. This
is why nitro compounds are often yellow.

3. Explain the regiospecific nitration at C-3 in benzaldehyde.

Regiospecific only forms one product that’s why the pi bond of the ring will attack NO 2 and will
generate a cabocation. Hydrogen will be attacked by the base and the bond of the hydrogen will
alienate the positively charged ion.

4. What is the reason of washing the petroleum ether solution with saturated sodium
bicarbonate?

Saturated sodium bicarbonate was used for purification of the solution and the petroleum ether
was used for recrystallization.

Experiment 7

Prelab questions

1. Describe the aldol reaction.

Aldol reactions or aldol addition reaction gives a product of both an aldehydic group and a
hydroxyl group. The mechanism for an aldol reaction has three steps. It begins with the
deprotonation of the position to form an enolate. The enolate serves as a nucleophile and
attacks an aldehyde. Then, t7he alkoxide ion that is formed is protonated to give the product.
2. When is the reaction stopped only at the β-hydroxy carbonyl intermediate? When does it go all
the way to the enone product?
 When the enolate of an aldehyde or a ketone reacts at the α-carbon with the carbonyl of
another molecule under basic or acidic conditions β-hydroxy aldehyde or ketone was obtained.
Otherwise, it will go all the way to the enone product.
3. What type of carbonyl compounds undergo the keto-enol tautomerism?
Keto-enol tautomers are constitutional isomers that are easily interconverted by a trace of acid
or base. Most aldehydes and ketones exist primarily in the keto form because of the greater
strength of the carbon-oxygen double bond.
4. What are the biochemical application(s) of the aldol reaction?
Aside from it demonstrates a solventless reaction, the aldol reaction has been used in the large-
scale production of the commodity chemical pentaerythritol and the synthesis of the heart
disease drug Lipitor. It is also exhibited in various biological processes such as glycolysis and the
glyoxylate cycle.
5. What are the advantages of solventless reactions?
Some advantages of utilizing solventless reactions are that the compounds are often sufficiently
pure to avoid extensive purification using chromatography, the reactions can be rapid, often
reaching substantial completion in several minutes compared to hours in organic solvents, and
the energy usage can be much lower.
6. What is “green synthesis”?
Solvent free synthesis or green synthesis doesn’t involve the use of solvents that harm the
environment. Green chemistry provides “Green” paths for different synthetic routes using non-
hazardous solvents and environmental friendly chemicals.

Postlab questions

1. What is the purpose of grinding in the reaction?

The mixture was grinded thoroughly so that the mixture become solid and the solid breaks up in
small particles.
2. Account for the mechanism of the reaction. Which carbonyl compound contains an α-acidic
hydrogen and is most likely to form the enol intermediate?
Aldehyde possesses an α proton and therefore can form an enolate.
3. Which carbonyl compound acts as the electrophile? Explain.
The second step of an aldol reaction involves nucleophilic addition of enolate to carbonyl group
of a second molecule of the aldehyde with the carbon in C=O bond acting as an electrophile.
4. What are the side-products formed during the course of the reaction? Draw their structure.

Were the side products of an aldol reaction with ketone as the starting material.
5. What impurities are washed away with water?
Water was used to wash away the water soluble impurity such a catalyst acid.

Experiment 8

Prelab questions

1. Provide literature collections of the many ways to prepare a Wittig reagent.

2. Sketch the general mechanism underlying the Wittig reaction.
3. What are the synthetic applications of the Wittig reaction?
4. What are the limitations of the Wittig reaction?