Exp095.JPG

Objective

To synthesize a Ugi adduct from 3,4-dimethoxybenzaldehyde, Furfurylamine, tertbutylisocyanide and Boc-Gly-OH in methanol using Ugi 4CR. This reaction is a scale-up of Exp095

Procedure

Dissolved 3,4-dimethoxybenzaldehyde (Veratradlehyde) (332 mg, 2 mmol) and Furfurylamine(FFA) (234.8 uL, 2.2 mmol, 10% excess ) in 2 mL methanol-d4 in a 2 mL volumetric flask. After two hours a solution of Boc-Gly-OH(350 mg, 2 mmol), and tert-butyl isocyanide(226 uL, 2 mmol) made up in 2 ml volutmeric flask in methanol-d4 was added to the preformed Imine. The product was recrystallized from a small amount of methanol and saved in a vial. Yield - 40%

Results

(Reactant NMRs from Exp054)
Veratradehyde
H NMR
C NMR
Furfurylamine
HNMR
CNMR
tert-Butyl isocyanide
H NMR
C NMR
Boc-Gly-OH
H NMR
C NMR
96A (x min After the addition of all 4 components)
H NMR
96B-1 (First batch of the product)
H NMR
96B-2 (Second bath of the product)
H NMR
96C

Discussion

Product accidentally lost.

Conclusion

Experiment aborted.

Log

2007-04-24

19:16 Madeup a solution of veratraldehyde and furfurylamine in 2 ml methanol-d4 in a volumetric flask.
21:10 Made up a solution of Boc-Glycine and tert-Butylisocyanide in a 2 mL volumetric flask in 2 mL methanol-d4.
21:16 Transferred the contents from the both the volumentric flasks to an erlenmeyer flask and swirled them for a few seconds to achieve mixing
21:59 Obtained H NMR of 96A
22:30 The reaction was put on a sonicator for 5min, when a the entire reaction mixture turned like a solid cake.


2007-04-25

20:00 Methanol (10 ml) was added to the solid product, filtered through a sintered galss funnel, and washed with another 5ml of methanol. The mother liquor was collected and left overnight for further crystallization.
20:50 The product was left under house vac overnight.

2007-04-26

14:30 Obtained 96B-1 (412 mg)
15:30 The mother liquor had developed crystals overnight, which was filtered, and washed with methanol (5 ml), 91B-2 was obtained (220 mg).
The remaining filterate was accumulated to see if any more product could be obtained.
18:59 Obtained H NMR of 96B-1 and 96B-2.
19:30 PRODUCT LOST
Since the fractions were contaminated with imine, aldehyde, etc. they were combined together in a one dram sotppered vial, methanol (4 mL) was added to the vail and stoppered again. No sooner the STOPPERED vial was put on a steam bath, the stopper flew over and the vial with the product submerged in the steam bath, the product started to float in dirty water in the steam bath. never heat a closed container
20:40 The dirty water containing the product was decanted in to a huge (2 L) separatory funnel and dichloromethane(~300 mL) was added to it, in the hope of extracting the lost product, the layers were separated. The brown organic layer was dried with MgSO4 (anhydrous) filtered again and dried on a high vac in a round bottom flask to dryness. The residue was taken up in methanol (5 mL).

Tags

3,4-dimethoxybenzaldehyde InChI=1/C9H10O3/c1-11-8-4-3-7(6-10)5-9(8)12-2/h3-6H,1-2H3
Furfurylamine InChI=1/C5H7NO/c6-4-5-2-1-3-7-5/h1-3H,4,6H2
tert-butyl isocyanide InChI=1/C5H9N/c1-5(2,3)6-4/h1-3H3
Boc-Gly-OH InChI=1/C7H13NO4/c1-7(2,3)12-6(11)8-4-5(9)10/h4H2,1-3H3,(H,8,11)(H,9,10)
Product InChI=1/C26H37N3O7/c1-25(2,3)28-23(31)22(17-11-12-19(33-7)20(14-17)34-8)29(16-18-10-9-13-35-18)21(30)15-27-24(32)36-26(4,5)6/h9-14,22H,15-16H2,1-8H3,(H,27,32)(H,28,31)