Advanced organic chemistry Lab – Alkylation of Sodium Saccharin

Prelab work:

1. Aim: The goal of this experiment is to investigate the nucleophilic attack of Sodium
Saccharin (N and O), which is alkylated by iodoethane in the aprotic solvent DMF (N, N-
Dimethylformamide). This reaction can produce two different products: o-ethyl saccharine
(Kinetically prefered product) and N-ethyl saccharine (thermodynamically prefered
product). The goal of this experiment is to figure out which one is the most important.
2.

3. Mass of Sodium Saccharine and Volume of Iodoethane with working out below

2.052 grammes of sodium saccharine were utilised.

Calculation: 10 mmol =.01 mol; formula: nm (number of mole) = Mass/Molar mass. nM
(number of moles) * Molar mass Equals mass
nM = mass (0.01mol) * Molecular weight (205.2 g/mol)
2.052g in mass

0.8 mL of iodoethane was utilised.

Formula = nM (number of mol) = Mass/Molar mass; Working out: 10mmol =.01mol; Formula
= nM (number of mol) = Mass/Molar mass Mass/Volume Equals Density.
nM (number of moles) * Molar mass Equals mass
Molecular mass = nM (.01) (156.0)Mass = 1.56g
Volume = mass/density; Density = mass/density
Mass (1.56g)/(1.950g/mL) = volume
0.8 mL volume

4A. The nucleophile N has a higher thermodynamic advantage.

E(Broken) – E(Broken) – E(Broken) – E(Broken) – E(Broken) – (Formed)

N – ethyl saccharine is a sweetener made from N – ethyl Enthalpy of Bonds: Enthalpy of

Bonds = E (No bonds broken) – E (N-C: 73)
Enthalpy of Bonding = 0 - 73
Enthalpy of Bonding = -73kcal/mol

Saccharine O-Ethyl Bond Enthalpy = E (C=o: 179) – E (N=C: 147 + O-C: 86) Bond Enthalpy = E
(C=o: 179) – E (N=C: 147 + O-C: 86) Bond Enthalpy = E (N=C: 147 + O-C:
Enthalpy of Bonding = 179 – (147 + 86)
Enthalpy of Bonding = -54kcal/mol

Because its bond energy is -73kcal/mol, which is lower than that of O-Ethyl Saccharin, N-
Ethyl Saccharin is a more stable and preferable product. As a result, the nucleophilicity of N
is increased.

4B. Reaction mechanism

4C.

Determining ratio.

On the chemical shift, you'd start by figuring out which molecule is the most critical. As in
the 10 minute 1H NMR 60deg experiment. Important chemical shifts include 3.8 (N-ethyl)
and 4.5 (benzene) (O-ethyl). Because the multiplicity is a quartet, it comes after ch3 (n+1).
Finally, divide the integration by the lowest integration, with the lowest integration
equalling 1 and the greatest integration equalling the output produced when the lowest
integration equals 1. (2020, Dr. Chris Schaller)
1:4.18 indicates that for every 1 (O-ethyl) molecule created, 4.18 (N-ethyl) molecules are
formed.
Melting point profile.

The melting point profile is used to determine the purity of a product fast. The melting
points of N-ethyl (95Co) and O-ethyl (211Co) (Zubrick, J. W, 1997) are very different,
therefore if the final product melts at 95 +/- 3-5Co, it is not O-ethyl, which has a melting
point of 211Co, and the end product must be N-ethyl. The final product is then refined by IR
and 1H NMR.
4D.

IR trends

The large peaks at 3361.59 and 3487.63 imply an OH and NH; this is a tautomerisation of
sodium saccharin. OH (3550-3200 wide) and NH (3350-3310 wide).

60Co @ 10mins is the title of this video.

- There is a peak at 1686 indicating the formation of an amide bond (1700 – 1650) that was
not seen in the IR of Sodium saccharin, indicating the formation of an N-ethyl derivative.
However, a prominent 3376.84 broad peak indicates the presence of leftover OH
molecules (3550 – 3200). Continuing, this shows that the reaction is still taking place, as
higher temperatures are required to get the entire N-ethyl product.
Title: 60Co @ 30mins

- The 3376.85 is no longer present, suggesting that there are no more OH molecules in the
product. Meanwhile, a new peak has emerged at 2981.70, indicating the creation of an
aliphatic carbon (3100-3000), implying complete product formation. There is a persistent
amide peak, with peak 1196.26 indicating the production of O-C ether (1200-1000). This
could indicate the presence of both N-ethyl and O-ethyl compounds.

80Co for 10 minutes and 80Co for 30 minutes

- With a blend of products O-ethyl saccharin and N-ethyl saccharin, the peaks remain the
same, with no new apparent product formation.

1H NMR 60Co @ 10mins - 4.18 N-ethyl is generated for every 1 O-ethyl product. Given
that O-ethyl is a kinetically prefered product, this is a large amount.
1H NMR 60Co @ 30mins - There is 4.48 N-ethyl for every 1 O-ethyl product produced.
Although there isn't a large increase in product, N-ethyl is projected to appreciate with
time.
1H NMR 80Co @ 10mins - There is now a ratio of 1:4.60, which shows a significant
increase in N-product yield as compared to the product yield at 60Co @ 30mins and 60Co
@ 10mins. This could be due to the fact that N-ethyl is a thermodynamically prefered
product.

1H NMR 80Co @ 30mins - The ratio is 1:5.37, and the N-ethyl product yield has increased
noticeably. As the reaction temperature and time rise, the yield of N-ethyl product
increases as well.

Graph 1: A linear relationship of ratio of products and series of compound all equal the
product yield of O-ethyl of 1.

%Yield
The experimental yield is not given to calculate a percent yield.
However, theoretical percent yield can be determined for each condition.

Conclusion:
Finally, the end result is a combination of O-ethyl saccharine and N-ethyl saccharine. N-ethyl
saccharine, on the other hand, will be the most produced as compared to O-ethyl
saccharine. This is due to the N-ethyl product's thermodynamic advantage, which needs less
energy to generate and is more stable at lower energies. Because there was no
experimental melting point, the product can be determined by conducting a melting point
test. Despite the fact that both chemicals will be produced, it is only reasonable to
anticipate that N-ethyl will have a higher yield.