----Benzene, r.t ----->




Objective

To study the kinetics of a Ugi reaction in benzene

Procedure



Results

HNMR of 1,1,3,3-tetramethylbutylisocyanide
UCExp246 Spreadsheet
Integrations-1
SAMS for UCExp246
UCExp246-1A HNMR
Phenanthrene-9-carboxaldehyde in benzene
01min
02min
04min
08min
15min
16min
26min
28min
30min
32min
40min
50min
1h33min
1h42min
1h50min
2h00min
2h08min
2h48min
4h20min
5h50min
20h43min
28h00min

UCExp246-2A
22min
49min
1h28min
1h33min
1h43min
1h50min
UCExp246-3A
3min
5min
7min
09min
22min
28min
34min
50min
58min
1h00min
1h16min
19h26min
61h43min

246-4A HNMR


Discussion

Calculations based on SAMS method indicate the concentration of phenanthrene-9-carboxaldehyde in the solution to be 0.66M insted of 0.6M.
Change in the concentration of the aldehyde is observed despite an accurate measurement was performed while weighing and solution making. The micro-pipette used had been recently calibrated. Evaporation of the solvent (benzene) during the transfer in to the NMR tube may have resulted in an increase in the concentration of the aldehyde to 0.66M. Therefore this concentration was taken as the starting concentration of the aldehyde.
UCExp246-i.jpg

Conclusion

Log

2009-08-20
10:20 Obtained a NMR tube coaxial insert.
10:40 Made-up a 0.6M solution of phenanthrene-9-carboxaldehyde by dissolving 124mg (0.6mmol) in benzene in a 1mL volumetric flask.
11:00 Made-up a 3M solution of phenylacetic acid by dissolving 409mg (3mmol) in benzene in a 1mL volumetric flask.
15:00 Pipetted out 167uL (0.1mmol) of the 0.6M aldehyde solution in to the inner tube. Pipetted out 150uL DMSO-d6 in to the outer tube. Capped both the tubes immediately after placing the liquids in them.
15:09 Obtained HNMR of phenanthrene-9-carboxaldehyde in benzene.
15:10 Pipetted out furfurylamine (8.83uL) in to the inner tube containing the aldehyde. The reaction mixture will now be referred to as UCExp246-1A
15:11 Obtained HNMR of the the solution- UCExp246-1A-1min, only one transient and a relaxation delay of 50s -01min
15:12 Obtained HNMR of the the solution- UCExp246-1A-2min, only one transient and a relaxation delay of 50s - 02min
15:14 Obtained HNMR of the the solution- UCExp246-1A-4min, only one transient and a relaxation delay of 50s - 04min
15:18 Obtained HNMR of the the solution- UCExp246-1A-8min, only one transient and a relaxation delay of 50s - 08min
15:25 Obtained HNMR of the the solution- UCExp246-1A-15min, four transient and a relaxation delay of 50s - 15min
15:26 Obtained HNMR of the the solution- UCExp246-1A-16min, only one transient and a relaxation delay of 50s - 16min
15:36 Obtained HNMR of the the solution- UCExp246-1A-26min, four transient and a relaxation delay of 50s - 26min
15:38 Obtained HNMR of the the solution- UCExp246-1A-28min, only one transient and a relaxation delay of 50s - 28min
15:40 Obtained HNMR of the the solution- UCExp246-1A-30min, only one transient and a relaxation delay of 50s - 30min
15:42 Obtained HNMR of the the solution- UCExp246-1A-32min, only one transient and a relaxation delay of 50s - 32min
15:50 Obtained HNMR of the the solution- UCExp246-1A-40min, four transient and a relaxation delay of 50s - 40min
16:00 Obtained HNMR of the the solution- UCExp246-1A-50min, four transient and a relaxation delay of 50s - 50min
16:43 Obtained HNMR of the the solution- UCExp246-1A-1h33min, four transient and a relaxation delay of 50s - 1h33min
16:52 Obtained HNMR of the the solution- UCExp246-1A-1h42min, four transient and a relaxation delay of 50s - 1h42min
17:10 Obtained HNMR of the the solution- UCExp246-1A-2h, four transient and a relaxation delay of 50s - 2h
17:18 Obtained HNMR of the the solution- UCExp246-1A-2h08min, four transient and a relaxation delay of 50s- 2h08min
17:58 Obtained HNMR of the the solution- UCExp246-1A-2h48n, four transient and a relaxation delay of 50s - 2h48min
19:30 Obtained HNMR of the the solution- UCExp246-1A-4h20min, four transient and a relaxation delay of 50s - 4h20min
21:00 Obtained HNMR of the solution - UCExp246-1A-5h50min, four transients and a relaxation delay of 50s - 5h50min
2009-08-21
11:53 Obtained HNMR of the solution - UCExp246-1A-20h43min, four transients and a relaxation delay of 50s - 20h43min
19:10 Obtained HNMR of the solution - UCExp246-1A-28h, four transients and a relaxation delay of 50s - 28h
19:15 Pipetted out phenylacetic acid (33.4ul, 3M in benzene) in to the inner tube of the NMR set of tubes containing the reaction mixture. The solution in the tube will now be referred to as UCExp246-2A
19:16 Placed the tube in the instrument..unable to achieve lock or obtain a decent sepctrum..shimmed over again
19:38 Obtained an HNMR, UCExp246-2A-22min
20:05 Obtained an HNMR, UCExp246-2A-49min
20:43 Obtained an HNMR, UCExp246-2A-1h28min
20:48 Obtained an HNMR, UCExp246-2A-1h33min
20:58 Obtained an HNMR, UCExp246-2A-1h43min.
21:05 Obtained an HNMR, UCExp246-2A-1h50min
21:12 Pipetted out 1,1,3,3-tetramethylbutylisocyanide (17.5uL, 0.1mmol). The reaction mixture will now be referred to as UCExp246-3A
21:15 Obtained an HNMR of UCExp246-3A-3min
21:17 Obtained an HNMR of UCExp246-3A-5min
21:19 Obtained an HNMR of UCExp246-3A-7min
21:20 Obtained an HNMR of UCExp246-3A-9min
21:34 Obtained an HNMR of UCExp246-3A-22min
21:40 Obtained an HNMR of UCExp246-3A-28min
22:02 Obtained an HNMR of UCExp246-3A-50min
22:10 Obtained an HNMR of UCExp246-3A-58min
22:28 Obtained an HNMR of UCExp246-3A-1h16min
2009-08-22
16:38 Obtained an HNMR of UCExp246-3A-19h26min
2009-08-24
10:43 Obtained an HNMR of UCExp246-3A-61h43min
2009-08-25
12:02 Obtained an HNMR of UCExp246-3A-86h50min
12:22 Obtained an HNMR of UCExp246-3A-87h10min
2009-08-26
07:34 Obtained an HNMR of UCExp246-3A-106h22min
2009-08-27
08:08 Obtained an HNMR of UCExp246-3A-118h56min
2009-08-31
11:00 Poured the contents of the sealed NMR tube in to a one dram vial, added ~2mL benzene to it.
11:10 Added 1mL 1M HCl (aq) to the vial, vortexed it for 15s and let it separate out.
11:20 Removed the bottom aqueous layer carefully using a glass pipette. Then added another 1mL 1M HCl (aq.) and vortexed the vial again for about 15s, after the layer separated out, the bottom aqueous layer was once again removed with the pipette.
11:40 Now added 1mL of 10% NaOH (aq) , vortexed the solution again for approximately 15s, and then removed the bottom aq. layer with a pipette. Repeated the wash with another 1mL 10% NaOH (aq).
11:55 Pipetted in to the vial 1mL saturated brine solution, vortexed, left the vial to settle down and separated the layers.
12:05 Added about 1g of anydrous MgSO4 to the vial. Vortexed it again, centrifuged and decanted the clear supernatant.
12:15 Washed MgSO4 in the vial with benzene (1mL), centrifuged and decanted the supernatant in the previously collected supernatant.
12:30 The combined supernatant were then set under a gentle flow of N2 to remove solvent (benzene). This was done to concentrate the product...by evaporating extra solvent..
14:00 Obtained an yellow oily liquid, this liquid is now labeled 246-4A
14:10 Dissolved246-4A in DMSO-d6 and obtained an HNMR