Exp113-i.JPG

Objective

To synthesize the Ugi product (086B)from benzaldehyde, 5-methylfurfurylamine, tert-butyl isocyanide and Boc-Gly-OH in methanol via a 4CR Ugi reaction using the Eppendorf protocol (EXPLAN005)

Procedure

To a 1.5 mL Eppendorf tube were added methanol (500 uL), 5-methylfurfurylamine(5-MFA) (56 uL, 0.5 mmol), benzaldehyde (51 uL, 0.5 mmol), Boc-Gly-OH(88 mg, 0.5 mmol), and tert-butyl isocyanide (57 uL, 0.5 mmol). The compounds were added in that order, with a 15 s vortexing (Fisher Vortex Genie 2) after each addition. After 24 hours, a solid formed and the tube was vortexed for 15 s then centrifuged at 14000 RPM for 60 s.This process will continue two more times, with the addition of methanol (500uL) each time before mixing. The resulting solution will be put under high vac in the opened tube.
Characterization of 113B:(C25H35N3O5) White crystals; HNMR (external image delta.gif ppm, CDCl3) 1.32 (s, 9H), 1.44 (s, 9H), 2.12 (s, 3H), 4.19 (s, 2H), 4.43 (s, 2H), 5.48 (s, 1H), 5.57 (s, 1H), 5.68 (s, 1H), 5.72 (s, 1H), 5.84 (s, 1H), 7.28 (s, 5H). Yield = 31%


Results

Benzaldehyde
H NMR
C NMR
5-methylfurfurylamine
H NMR
C NMR
tert-butyl isocyanide
H NMR
C NMR
Boc-Gly-OH
H NMR
C NMR

113A
HNMR (still wet with methanol and acetone- let dry on high vac in vial (note pressure))
113B
HNMR(no acetone but still wet with methanol - re-evaporate under high vac, measuring pressure)

Discussion



Conclusion

A synthesis of the ugi product was successfully accomplished.


Log

2007-07-17

13:55 Weighed 1.5mL Eppendorf tube (837.6mg) and labeled it
14:00 Filled tube with methanol (500uL), solution was clear
14:02 Measured 5-methylfufurylamine (56uL) and added it to solution, solution was light orange and translucent
14:03 Mechanically mixed on vortex for 15 seconds
14:04 Measured benzaldehyde (51uL) and added it to solution
14:05 Mechanically mixed on vortex for 15 seconds
14:09 Weighed out 88 mg of Boc-Gly-OH
14:10 Added Boc-Gly-OH to solution, solution turned a dark orange color
14:10 Mechanically mixed on vortex for 15 seconds
14:12 Measured tert-butyl isocyanide (57uL) and added it to solution, solution turned a red-orange color
14:13 Mechanically mixed on vortex for 15 seconds
14:13 Allowed the solution to sit undisturbed in the 1.5mL Eppendorf tube
14:45 Observed white crystals formed along the sides of the Eppendorf tube

2007-07-18

13:30 White crystals formed throughout Eppendorf tube
14:40 Precipitate formed, mixed on vortex for 15 seconds
14:45 Centrifuged at 14000 RPM for 60 seconds, then discarded supernatant
14:48 Added methanol (500uL), mechanically mixed on vortex for 15 seconds
14:50 Centrifuged at 14000 RPM for 60 seconds, then discarded supernatant
14:53 Added methanol (500uL), mechanically mixed on vortex for 15 seconds
14:55 Centrifuged at 14000 RPM for 60 seconds, then discarded supernatant
15:05 Put open tube under high vac (pressure?)
15:40 Weighed tube, came out to 1011mg
16:00 Emptied tube, laid out contents on filter paper to dry (113A) the powder was still wet after 35 mins on the high vac?

2007-07-19

14:35 Placed 0.01g of solid product into an NMR tube with CDCl3 (600uL)
14:40 Obtained an H NMR
16:30 Added the remaining product (0.093g) to the NMR tube

2007-07-20

17:00 Poured solution from the NMR tube into a vial, covered with aluminium foil and poked holes at the top

2007-07-23

11:14 Observed a dry solution in the vial, placed vial into high vac (pressure: )
12:15 Turned off high vac
15:36 Weighed vial with product (4.751g)
15:55 Washed vial with CDCl3 (800uL) and inserted remaining solution into an NMR tube (solid product from vial included, weighing 0.0714g)
16:05 Weighed empty vial (4.6796g)
crytals_copy.jpg

Tags

86BInChI=1/C25H35N3O5/c1-17-13-14-19(32-17)16-28(20(29)15-26-23(31)33-25(5,6)7) 21(18-11-9-8-10-12-18)22(30)27-24(2,3)4/h8-14,21H,15-16H2,1-7H3,(H,26,31)(H,27,30)
benzaldehydeInChI=1/C7H6O/c8-6-7-4-2-1-3-5-7/h1-6H
5-methylfurfurylamine InChI=1/C6H9NO/c1-5-2-3-6(4-7)8-5/h2-3H,4,7H2,1H3
tert-butyl isocyanideInChI=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)