exp029a.JPG

Objective

To obtain the Ugi product in methanol using the method described here.

Procedure

To separate vials was added 5-methylfurfurylamine(111 uL, 1 mmol) piperonal(150mg, 1 mmol), benzylisocyanide (I21 uL, 1 mmol), and Boc-Gly-OH (175 mg, 1 mmol) and diluted to 1 mL with methanol. Added solutions together in a separate one dram vial and mixed them together. Allowed mixture to sit for 24 hrs. Evapoated on high vacuum. Added 2 ml CDCl3 to dried product and transfered to an NMR tube using a Pasteur pipet.

Results

Characterization of 29A

476.3 mg
C13 NMR S/N needs to be better
HNMR

Discussion

HNMR

The region between 3-4.5 ppm is expected to be "peak rich" because the majority of the starting materials contain protons that are expected to come into resonance in this region:
5-Methylfurfurylamine (methylene at 3.7)
Boc-Gly-OH (methylene at 4.0)
Benzylisocyanide (methylene at 4.6)
Because of this it is hard to say whether or not the starting materials have been converted to the Ugi Product. This can also be said about the number of aromatic rings in all of the starting materials. It can be said that the HNMR for 29A is showing peaks consistent with that of piperonal indicating that the aldehyde may still be present. This is evidenced by a singlet peak at 9.8.

CMR

S/N ratio needs improvement but will be inconclusive at this point because of the length of time that the reaction has been sitting.

Conclusion

Using only proton NMR it is hard to successfully conclude whether the Ugi product was obtained. In the future it would be best to monitor the reaction by taking NMR's between the additions of each component in order to tell whether product is forming.

Log

2006-10-04

13:35 Mixed 5-methylfurfurylamine, piperonal, and Boc-Gly-OH solutions (yellow) at room temperature. Vial was vigorously shaken.
13:45 Added 1ml of benzylisocyanide solution. Vial was vigorously shaken.

2006-10-05

18:30 Evaporated solvent using rotovap on high vacuum to yield 29A.

2006-10-06

13:00 Took C13 NMR and proton NMR of 29A

Tags

Benzylisocyanide InChI=1/C8H7N/c1-9-7-8-5-3-2-4-6-8/h2-6H,7H2
PiperonalInChI=1/C8H6O3/c9-4-6-1-2-7-8(3-6)11-5-10-7/h1-4H,5H2
Boc-Gly-OHInChI=1/C7H13NO4/c1-7(2,3)12-6(11)8-4-5(9)10/h4H2,1-3H3,(H,8,11)(H,9,10)
5-methylfurfurylamineInChI=1/C6H9NO/c1-5-2-3-6(4-7)8-5/h2-3H,4,7H2,1H3
ugi019:InChI=1/C29H33N3O7/c1-19-10-12-22(38-19)17-32(25(33)16-31-28(35)39-29(2,3)4)26(21-11-13-23-24(14-21)37-18-36-23)27(34)30-15-20-8-6-5-7-9-20/h5-14,26H,15-18H2,1-4H3,(H,30,34)(H,31,35)
DKP019InChI=1/C17H16N2O5/c1-10-2-4-12(24-10)8-19-15(20)7-18-17(21)16(19)11-3-5-13-14(6-11)23-9-22-13/h2-6,16H,7-9H2,1H3,(H,18,21)