The Aldehyde Anigma

Objective

The objective for this experiment was to use nuclear magnetic resonance and infrared resonance
spectroscopy to correctly identify the products and to deduce the starting products from the results.

Mechanisms
Procedure and Observations

Procedure Observations

Add .5ml of unknown and 1.5ml of 11M KOH Unknown B

solution to a 10 ml round bottom flask.

Reflux at 90-100C for 1-1.5 Refluxed for 1.5hr

TLC was taken of the product to check for Starting material Rf:
completeness.
Product Rf:

4ml cold DI water was added to reaction and the

aqueous layer was extracted twice washing with
4mL of ethyl acetate. The aqueous layer was set in
an ice bath.

2mL cold DI water was added to chilled aqueous Precipitate formed. White crystals.
layer. 6mL of 6M HCl was added. The solution was
vacuum filtered and allowed to dry. Final aq. Mass:

Aq melting point: N/A

Organic Layers were returned to the sep. funnel Mass of round bottom.
and was washed with 5% sodium bicarbonate
solution and was then dried over anhydrous Substance after rotovap looks oily
Na2SO4 and filtered into a tared 25 mL round Mass of rb and organic
bottom flask. The solvent was evaporated using
the rotovap and then was placed on a vacuum to
remove last traces of solvent.
Final organic mass:

HNMR and CNMR and IR Could not attain IR for either product

Results

Unknown B was found to be p-tolualdehyde. The two products were p-toluic acid

(aq.) and p-methylbenzyl alcohol (org.)

There was not enough aqueous product to run melting point or HNMR. The aqueous product was
inferred after identifying the starting product.
Theoretical yield

1.5mL KOH 11mol 1L 1 mol =0.0165

mol KOH
1L 1000mL 1 mol

0.5 mL p- 1mol 1.019 g 1 mol alcohol =0.0021 mol alcohol

tolualdehyde
120.149 g 1mL 2 mol
aldehyde
*limiting factor

0.5 mL p- 1mol 1.019 g 1 mol =0.0021 mol carboxylic

tolualdehyde carboxylic acid acid
120.149 g 1mL 2 mol
aldehyde
*limiting factor

Actual Yield

Organic

.2521g p-toluic 1mol =0.0018

acid mol

136.1 g

Aqueous

N/A

Percent yield

Organic

.0018/.0021= 88%

Aqueous

N/A
Organic HNMR table

Assignment Cheimical Shift j-Values Splitting Integration

Ha 7.4 d 2
Hb 7.296 d 2
Hc 4.662 s 1
Hd 2.370 s 3

CNMR table

Aqueous

Assignment Peak (ppm)

C1 172.151
C2 144.623
C3 130.249
C4 129.212
C5 126.618
C6 21.756

Organic

Assignment Peak (ppm)

C1 138.024
C2 137.215
C3 129.181
C4 127.121
C5 64.993
C6 21.146

Conclusion

In the organic CNMR spectrum there are 6 peaks. Two peaks are much taller than the others, indicating
symmetrical carbons. In the organic HNMR there is a doublet of doublets around 7.25. This also
indicates that there is some symmetry in the organic molecule. The integration values of 2 on those
protons also indicate symmetry for the hydrogens. Because there is symmetry, that means that the
product must be para substituted. The single proton with the 4.662 shift has to be connected to the
carboxylic acid. The last peak is a singlet with an integration of three. The singlet indicates that these
three protons are all symmetcal, therefore it can be concluded that the unknown R-group is a methyl
group.
Because the reaction was supposed to form a carboxylic acid and an alcohol with the same R- group, it
can be inferred that the aqueous product is and that the unknown starting product had to have been.

Because we knew that we were dealing with an aldehyde with a benzene ring with tert-butyl attached
we knew there had to be eleven carbons. The CNMR of the aqueous product shows seven unique
carbons. This means that there had to be two pairs of symmetrical carbons on the benzene ring. The
only configuration that allowed for two pairs of equivalent carbons is the para configuration. The peaks
from 2870.3 to 2965.9 on the IR spectra confirm the presence of a carboxylic acid. The observed melting
point of the aqueous layer, 161.5C, compared with the known melting point of p-t-butyl-benzoic acid
also confirms the identity of the aqueous product.

Working backwards from the two products, we can conclude that the Unknown A is p-tert-
butylbenzaldehyde.