Objective

To synthesize a Ugi adduct from furfurylamine, phenanthrene-9-carboxaldehyde, phenyl acetic acid and n-butyl isocyanide in THF and methanol using Ugi 4CR at 0.8M and 1M concentrations respectively.

Procedure

Results

Pictures
UCExp237-1a (methanol after addition of all reactants)
UCExp237-2a (THF after addition of all reactants)
MGUCExp237-1A-2 (methanol- second day)
IMGUCExp237-2A-2(THF- second day)
IMGUCExp237-2A-3 (THF-fourth day)
Spreadsheet

Discussion

Due to an error, the reaction in THF could not be carried out at 1M conc of each component. The final conc of each component in vial 237-2 was calculated to be 0.807M [I think that probably will work - if not we'll do it at the higher concentration next time JCB]
The Ugi product from the reactions will be used to measure solubility in different non-aqueous solvents.
A solid was obtained in UCExp237-2, reaction run in THF after four days. This may have occurred either because a) the reaction is slow in THF b) ppt formation takes longer than in methanol because the product is more soluble in THF than in methanol (assuming the rate of the Ugi reaction in THF is similar as in methanol) and c) because some of the solvent THF might have, some how evaporated from the vial (although tightly capped) causing the product to ppt out.


Log

2009-07-08

20:00 In a 10mL vial labeled 237-1 weighed out phenanthrene-9-carboxaldehyde (4mmol, 824.9mg).
21:10 Pipetted out methanol (2.0825mL) in to the vial containing the aldehyde, vortexed for 1min, the solid did not dissolve.
21:20 Pipetted-out furfurylamine (4mmol, 353.5uL) in to the vial 237-1. Vortexed for 30s, solid did not dissolve
21:25 Weighed out 2-phenylacetic acid (4mmol, 544.6mg), added it to vial 237, vortexed for 2min, almost all of the solid went into solution except for a couple of flakes.
21:40 Pipetted out 1-butylisocyanide (4mmol, 418.3uL) into vial 237-1. Vortexed the solution for 30s and left the solution in a fume hood at room temp.
21:55 In to a half dram vial, labeled 237-2 weighed out phenanthrene-9-carboxaldehyde (0.2mmol, 41.2mg) and dissolved it in 152.3uL THF...
22:00 Pipetted-out furfurylamine (0.2mmol, 17.6uL) in to the vial 237-2. Vortexed for 30s.
22:05 Weighed out 2-phenylacetic acid (0.2mmol, 27.2mg), added it to vial 237-2. Vortexed for 30s.
22:10 Pipetted out 1-butylisocyanide (0.2mmol, 20.9uL) into vial 237-2. Vortexed the solution for 30s and left the solution in a fume hood at room temp.
22:15 Obtained pictures of the solutions. UCEx[237-1a and UCExp237-2a

2009-07-09

12:00 Vial 237-2 did not form any solid ppt yet., A picture of the both vials was taken (IMGUCExp237-1A-2 and IMGUCExp237-2A-2)
15:00 Vial 237-1 had developed yellow solid mass. A picture was taken and the methanol (~5mL) was added to the vial vortexed for ~30s.
15:20 The yellow did not dissolve in methanol, The supernatant was filtered off by suction filtration The yellow residue collected, now called UCExp237-1A smelled intensely of butylisocyanide.Therefore it was subjected to recrystallization.
15:35 To the yellow solid UCExp237-1A, 25mL fresh methanol was added in a 500mL beaker set to heat on a hot plate.
15:45 After heating for some time, it completely dissolved in methanol.
16:20 The beaker was cooled down and parafilmed for a slow recrystallization.
21:00 Vial 237-2 did not develop any ppt yet...The solution remained clear.

2009-07-11

14:00 Solid had formed from the solution UCExp237-1A which was set for recrystallization....The solid was filtered off and an off white solid solid was obtained. This solid collected on the filter paper was left to dry in a vacuum desiccator. The mother liquor (UCExp237-1A-2) was collected
19:00 Removed the solid on the filter paper from the desiccator and obtained UCExp237-1B (570m).
19:20 Interestingly, some solid has appeared in the vial UCExp237-2, which contained the reaction components in THF.
20:45 Obtained a picture of UCExp237-2, this pic is labeled IMGUCExp237-2A-3