Jiwani Peters

01/25/2023
Experiment 1: Reduction of Camphor

Objective:

In this laboratory experiment, sodium borohydride, a potent base, and methanol are

used to watch camphor, a naturally occurring ketone, be converted into the alcohols borneol

and isoborneol and using NMR we will determine the ratio of Isoborneol to Borneol in the

product.

Physical Constant Data Table:

IUPAC Structure Density Molecular Mass Moles

NAME or (g/ml) Weight
Molecular (g/mol^-1)
Formula

Camphor N/A 152.23 g/mol 0.25 g 0.001642251

(C10H16O) 85 moles

Methanol 0.792 g/ml 32.04 g/mol 1.5 ml 0.046816479

(CH3OH) 4 moles

Sodium N/A 37.83 g/mol 0.25 g 0.006608511

Borohydride 76 moles
(NaBH4)

Dichlorometh 1.33 g/ml 84.93 g/mol 10 ml 0.117744024

ane (CH2Cl2) 49

Sodium 2.66 g/ml 142.04 g/mol 0.5 g 0.003520135

sulfate 17 moles
(Na2SO4)
SDS:

- Camphor:

Flammable solids

Acute toxicity, Inhalation

Skin irritation

Serious eye damage

Skin sensitization

Specific target organ toxicity - single exposure,

Short-term (acute) aquatic hazard

Long-term (chronic) aquatic hazard

- Sodium Borohydride:

Chemicals which, in contact with water, emit flammable gasses

Acute toxicity, Oral

Skin corrosion

Serious eye damage

Reproductive toxicity

- Methanol:

Flammable liquids

Acute toxicity, Oral

Acute toxicity, Inhalation

Acute toxicity, Dermal

Specific target organ toxicity - single exposure Eyes, Central nervous system

Introduction:
 It is significant to recognize the power of sodium borohydride in this reaction because it

can convert primary and secondary alcohols from both aldehydes and ketones. When

attempting to reduce the oxygens in carboxylic acids or esters, however, it falls short and must

be supplemented with a more potent chemical, like lithium aluminum hydride. Furthermore, the

sodium borohydride acts as a tool to attack the CO double bond from above (exo), forming the

bond's first CH bond in the process. However, when the CH bond is present, the charge of the

CO bond changes to a negative charge as a result of the movement of electrons, making it

more receptive to accepting a hydride in order to obtain the alcohol group. Due to the steric

hindrance of camphor structure, the exo attack renders the formation of Borneol. This means

that the endo attack has the least steric hindrance making Isoborneol the major product while

making Borneol the minor product. Using IR Spectra, which enables us to see the presence of

function groups that should be present in both Borneol and Isoborneol, we first assess the

validity of our reaction. Using the integrated numbers of each peak, we can calculate the

percent composition of the product with respect to Borneol and Isoborneol. The next step is to

determine the mixture of our product using NMR Spectra, which highlights the presence of

hydrogens near something electronegative.

Chemicals and Equipment:

- Camphor 0.25 g

- Methanol 1.5 ml

- Sodium Borohydride 0.25 g

- 10 mL Dichloromethane

- 0.5 g Na2SO4

- Filtering paper

- Rubber stopper

- Hot plate
 - Oven

- Büchner flask and funnel

- Clamps & Retort Stand

- Rubber tubes

Methods and Procedure:

The experiment was started by combining 250 mg of camphor with 1.5 ml of methanol in

a 50 mL Erlenmeyer flask. I used a glass stirring rod to stir the mixture and make sure the

camphor was completely dissolved. The highly flammable gas NaBH4 was then added to the

mixture, being careful to add it slowly and concisely to prevent any mishaps. I heated the

mixture in a hot water bath for two minutes to speed up the reaction. During this reaction we

saw that instead of the mixture clumping up after it heated, it actually crystallized so we had to

use a glass stirring rod to break apart the crystals.

I carefully added 10 ml of ice-cold water to the mixture after it had been heated in order

to cool it off, which caused a crude product to form and gather through vacuum filtration. It took

roughly 10 minutes of vacuum filtration to dry the product sufficiently for it to dissolve precisely

in 10 ml of dichloromethane. However in this step, we accidentally spilled water into the flask.

But since DCM is non-polar and water is polar, the mixture did not mix and created a layer. The

top layer was water since water has a lower density than DCM so we pipetted out the water to

save the DCM. Then I used anhydrous NaSO4 as a drying agent to stop water from absorbing

into or escaping from the product.

I thought the solution was a bit hazy when I first saw it. But after a few more minutes, the

answer started to make sense. I had the purified product left over after the solvent had

completely evaporated using a hot water bath.

Results and Observation:

Mass of the product:

Mass of the flask 26.50 grams

Mass of the flask with the product 26.64 grams

Mass of the product 0.14 grams

Melting Point:

Melting Point of Isoborneol 212-214 degrees celsius

Melting Point of Borneol 213 degrees celsius

Melting Point of mixture of Isoborneol and 198-203 degrees celsius

Borneol

Treatment of Results:

IR of the mixture of Borneol and Isoborneol:

The figure above shows the IR of the mixture of Isoborneol and Borneol. Both organic

substances have an alcohol group. We can see this O-H stretch in the peak 3383.86. OH
stretches are usually from 3500-3200 which shows that the OH group is present in the product.

The second indication we can analyze is the peak at 2949.92. This indicates the presence of a

CH sp3 stretch.

H1 NMR of the Product:

The above image shows the NMR of the product with the mixture of Isoborneol and Borneol. As

we can see, the PPM of Isoborneol is 4.5829 and the PPM of Borneol is 1.000. We can see that

the major product is Isoborneol. This is due to the fact that there is less steric hindrance in the

endo attack therefore making more of Isoborneol.

250 mg of Camphor

250 mg / 1000 = 0.25 g of camphor

Molecular weight: 152.23 g/mol

0.25 g / 152.23 g/mol = 0.00164225 moles of reactant

250 mg of NaBH4

250 mg / 1000 = 0.25 g of NaBH4

Molecular weight: 37.83 g/mol

0.25 g / 37.83 g/mol = 0.0066085 moles of reactant

Percent Yield:

Mass of the flask with the product (26.64 grams) - Mass of the flask (26.50 grams)

Mass of the Product = 0.14 grams

% yield = actual yield/theoretical yield *100%

(0.14 g / 0.00164225*154.25 g/mol) *100

0.55266707508*100

55% yield

Borneol: 1.000 / 5.5829 * 100 = 17.9%

Isoborneol: 4.5829 / 5.5829 * 100 = 82.1%

The ratio of Isoborneol to Borneol in the product is 4:1

4 C10H10O + NaBH4 + 4 H2O → 4 C10H18O + NaB(OH)4

Discussion and Conclusion:

We succeeded in reducing camphor to isoborneol and borneol, which made the experiment

successful in the end. The absence of a broad peak at 1750 cm-1 in the IR spectrum provided

evidence that no carbonyl group was present. The experiment was a success because the

broad peak at 3383.86 cm-1 indicated the presence of the O-H group (alcohol). The yield for the
product was 55 percent, which is not the next figure in terms of yield. Product loss during

filtration would be the element that affected my yield. Additional product loss happened due to

the fact that in the beginning of the experiment when stirring NaBH4 with Camphot, our reaction

crystallized fully rather than forming clumps. This made it hard for us to take out all the contents

from the flask. The range of the melting point measured was 198-203 degrees celsius. It is

outside the literature's range, which indicates that the product was pure, but it matches the

value of 212-214 °C in the literature. The peak around 3383.86, which displayed the OH group

and successfully demonstrated that the reduction was complete, was one of the significant

peaks in the IR spectrum. Since the C-O bond would show the product was tainted, it was not

present. Based on the IR, NMR, percent yield, melting point, and ratio results, the theory's

predictions did indeed match the data. However, due to our mistakes in the first part of the lab,

our product and yield ended up deviating heavily from the literature values. For example the

literature value of Isoborneol to Borneol is 85:15 while ours was 82.9:17.1. While this may seem

like a good result, our percent yield being 55 percent shows that the experiment wasn’t all that

successful.

The ratio of our products was roughly 83:17 (Isoborneol to Borneol) and the major

isomer obtained was Isoborneol.