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This preparation is an example of a catalytic transfer-hydrogenation. The reaction scheme for the hyPhysical Chemistry — Thermodynamics Chemistry Question

Preparation of 3-(4-methoxyphenyl)propanoic acid

This preparation is an example of a catalytic transfer-hydrogenation. The reaction scheme for the hydrogenation is as follows:
[VISUAL]
This hydrogenation in which ammonium formate serves as hydrogen source, is an alternative for the conventional catalytic hydrogenation using hydrogen gas. In both procedures Pd on charcoal is used as the catalyst.

Procedure
A magnetically stirred suspension of 4-methoxycinnamic acid (IUPAC name: E-3-(4-methoxyphenyl)prop-2-enoic acid) (450 mg) in water (7 cm 3 ) is treated slowly with concentrated aqueous ammonia (25%, 0.5 cm 3 ). After 5 min. palladium on charcoal catalyst (10%) and ammonium formate are added and the mixture is heated under reflux. The mixture gradually clears and the reaction is stopped after ca. 30 min. The completeness of the reaction is then checked by thin layer chromatography (TLC) plates (silica gel 60 F254) using heptane / ethyl acetate / formic acid in the ratio 99 : 99 : 2 as the eluent. The starting material is used as reference. If starting material is still present, the reaction mixture is heated for another 10 min. Then the reaction mixture is cooled to room temperature and filtered through a Hirsch funnel covered with a small piece of filter paper. The filter is washed four times with water (0.5 cm 3 ). The clear solution is then acidified with concentrated hydrochloric acid (c = 10 mol dm -3 ). It is needed ca 0.5 cm 3 of the acid to reach pH 2. (Check with pH paper.) A white precipitate is formed which is filtered off with a Hirsch filter, washed with water (10 cm 3 ) and partially dried. Whilst still slightly wet the product is taken up in heptane (10 cm 3 ) and the mixture is heated under reflux for 5 min. The obtained colorless solution is decanted. The residue is extracted twice with heptane (5 cm 3 ). The combined decanted fractions are heated to completely dissolve all material. The product is then allowed to crystallize by cooling in the a crushed ice bath. The crystals are collected by filtration, dried and weighed. The yield is calculated and the melting point is determined.
Note: This experiment can be carried out on a half scale with micro scale equipment described in this

Record the following data:
1. The mass of the product.
2. The yield of the product in the percentage of the theoretical yield (show your calculation).
3. The appearance of the crystals and their color.
4. The melting point of the crystals.
5. Copy your TLC plate on the date sheet and calculate the respective Rf values.

27.1.

Calculate the quantity of starting material in mmoles.

Model Answer

From the experiment.

27.2.

Is ammonium formate used in excess? If so, calculate its molar quantity.

Model Answer

From the experiment.

27.3.

Propose a catalytic cycle for the transfer hydrogenation process.
Hint: CO2 is formed during the reaction.

Model Answer

[VISUAL]

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