N-4-phenyl picolinamide -Gurung

In this experiment, we are trying to create one branched, N-4-phenyl picolinamide molecules from the reaction between picolinic acid and pheylisocyanate in presence of amine, diisopropylethylamine and solvent DMF, under standard conditions.

Reactant:

Reactant Used Ratio
Picolinic acid 0.932g 1.5
Phenylisocyanate 0.548ml 1
N,N-diisopropylethylamine 1.76ml 2

Synthesis:

Reactant Used Ratio
Picolinic acid 0.936g 1.5
Phenylisocyanate 0.550ml 1
N,N-diisopropylethylamine 1.757ml 2
DMF (Solvent) 245.40ml

Observation:

10th Sept 2012

Picolinic acid was dissolved in DMF, the resulting solution was colorless solution, followed by addition of isocyanate, which turned the solution to yellow, then we added the amine N,N-diisopropylethylamine, which did no visual change to the solution. The solution was left to mix overnight.

Added at 15:20

17th Sept 2012

Under vacuum, attempt was made to remove the solvent, DMF, from the solution, but since it took long time, it was left to evaporate in air overnight.

Started at 17:45

19th Sept 2012

After two days all the solvent had already evaporated, leaving pale while/yellow sold at the flask.

Image

24th Sept,2012

The solid was to be dissolved in methanol for TLC, but unfortunately an error was made where I added water instead of methanol. Then, I added methanol on the solution so that it was 50/50 water and methanol and proceeded with heating the solution. On heating all the solid particles dissolved.

The solution was then put in ice to induce crystallization. Few crystals were formed. After that, the crystallization was done under vacuum. The solid collected in the filter paper was labelled KG01.

Formation of crystals were also observed in the filtrate, so we proceeded to crystallize the solute from the filtrate under vacuum in second erlenmeyer flask, and the crystal obtained was labelled KG02.

25th Sept,2012

To test where the crystals were expected products or not, their melting ranges were taken and was found to be 228-234oC for both KG01 and KG02, which is pretty high than of N-4-phenyl picolinamide,72.6-74.0oC (ref. Sasaki, Crich.) we are trying to synthesize. This is also intriguing because none of the reactants also have such high melting range.

Chemical Melting point/range (oC)
Picolinic acid 137
Phenylisocyanate -30
N,N-Diisopropylethelamine <-50

source: MSDS sheet, http://www.sciencelab.com

Hoping that the expected products were still in the filtrate obtained from crystallization, I initiated evaporation of liquid to in air obtain the solid product (along with other possible impurities.)

3rd Sept,2012

All the liquid had evaporated leaving pale white/yellow solid similar to the one obtained at 19th Sept 2012.

The solid was dissolved in methanol, giving orange solution, and TLC test was conducted with solvent of 95% dichloromethane and 5% methanol.

Image

The sample does contain mixture of particles.

By looking at Dr Bodwin’s similar experiment and TLC of his sample in similar solvent,

Image

it’s reasonable to say the product is between the two reactants (bottom two in the plate), and it seems acetone (the top one), can get ride of those two reactants leaving the product.

Right now what we have left to do is to separate the product and find out it’s structure, and possibly of also KG01 and KG02.

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