Exp150-i.JPG


Objective

To synthesize a Ugi adduct from Phenanthrene-9-carboxaldehyde, benzylamine, Tert-butylisocyanide and Crotonic acid in methanol using Ugi 4CR. The target ugi product was first synthesized in our lab (Exp150). This is done in order to perform solubility test on the product.

Procedure

After charging a vial with methanol (1mL), phenanthrene-9-carboxaldehyde (0.5mmol), benzyl amine (0.5mmol) and crotonic acid (0.5mmol) was added to it. The solution was vortexed for 10min, until the solution became clear. To this t-butyl isocyanide (0.5mmol) was added to it. The solution was vortexed for 2min and left in the hood overnight.
Characterization of 214C: White powder; H-NMR (external image delta.gif ppm ppm, CDCl3) 1.39 (s, 9H), 1.77 (d, 3H J=6.3Hz), 4.79 (d, 1H, J=17.9 Hz), 4.88 (d, 1H, J=17.9 Hz), 5.67 (s, 1H), 6.18 (d, 1H, J=15.0 Hz), 6.33-6.81 (m, 4H), 6.88-7.23 (m 2H ), 7.36-7.74 (m, 4H), 7.80 (d,1H J=7.3 Hz), 7.90 (s 1H), 8.09 (d 1H J 12.2 Hz), 8.51 (t 2H J=12.8Hz); 13C NMR (external image delta.gif ppm, CDCl3) 18.1, 28.6, 49.0, 50.6, 51.7, 57.6, 94.6, 122.2, 122.4, 122.9, 124.2, 125.8, 126.6, 126.68, 127.1, 127.2, 128.7, 129.3, 130.1, 130.2, 130.4, 130.7, 30.9, 137.3, 143.4, 168.0, 169.9 ; IR (KBr, 1/cm): v = 3323, 3058, 2969, 1677, 1655, 1594, 1526, 1421, 722, 695; HRMS m/z calcd for C31H32N2O2 : 465.2542 [M+H] found 465.2448; C31H32N2O2Na 487.23614 [M+Na] found 487.23761; yield 34%

Results

214A-1, 214A-2
214B
214C
HNMR (500MHz)
HNMR (300MHz)
HNMR of 150D from EXP150
CNMR
All Protonated Carbons
DEPT
MS (FAB)
HRMS

Discussion

Based on the previous measurement of the solubility of phenanthrene-9-carboxaldehyde in methanol, it is not surprising that a clear solution can't be obtained (ONSCExp024) because it is soluble to an extent of only 0.078M in methanol.

Conclusion

A synthesis of the Ugi product was successful.

Log

2009-01-14

19:25 Added methanol (1mL) to a 5dram screwcap vial.
19:35 Added phenanthrene-9-carboxaldehyde 103.4mg ..tried to dissolve it by vortexing for 4min...unable to achieve complete dissolution.
19:45 Added benzylamine (54.6uL) to it. Vortexed for 30s
20:00 Added Crotonic acid (43.4mg) to it..vortexed for 9min..Most of the solid dissolved, however a small amount of oily fluid remained undissolved.
20:16 Obtained a picture of the solution, now called 214A
20:20 Added t-butylisocyanide (56.5uL) to the above solution..vortexed for 3min.
20:21 Obtained a picture of the solution..now called 214B
20:25 Left the reaction mixture (vial) in the hood for the reaction to complete..recorded the temperature-25C.

2009-01-15

10:57 The solution remains clear (PIC)
19:34 A very small amount of solid /precipitate has started to appear in the solution (PIC)

2009-01-16

10:28 A good amount of solid/precipitate has formed in the solution (PIC)
11:00 The solution (214B) was vortexed for 30s and centrifuged. The supernatant was decanted and to the residue was washed with methanol (300x 3). The supernatant was collected in to another vial..this is now referred to as 214D
12:30 The residue obtained after washing was left to dry in a vacuum desiccator.
16:30 The dry residue now called 214C (78.4mg- yield 33.7%)
22:00 Obtained a proton NMR of the residue by dissolving about 20mg of the solid in CDCl3 (0.6mL)
22:30 A DEPT run is being performed on the sample...with nt=8000, d1=3.

2009-01-17

11:00 Obtained a Carbon-13 NMR and a DEPT of Exp214C on a 300MHz Varian Inova.