Exp115

== =Objective= To monitor the synthesis of a Ugi adduct from furfural, methylamine, benzylisocyanide and α,4-dimethylphenylacetic acid by NMR spectroscopy. =Procedure= To a 2.0M solution of methylamine in methanol (250ul, 0.5 mmol) was added methanol-d4 (250uL) and furfural (41.5uL, 0.5 mmol) in an NMR tube. The imine formation was monitored by proton magnetic resonance spectroscopy. After twenty four hours α,4-dimethylphenylacetic acid (82.1mg, 0.5 mmol) and benzylisocyanide (60.5uL, 0.5 mmol) was added to it. The reaction was further monitored. =Results=

[|HNMR] [|CNMR] [|HNMR] [|HNMR] [|CNMR] [|H NMR] [|C NMR]
 * Furfural**
 * Methylamine** (1.0M Solution in 1:1 CH3OH : CD3OD)
 * α,4-dimethylphenylacetic**
 * Benzylisocyanide**

[|t = 5min] [|t = 7min] [|t = 4h 56min] [|t = 24h 39min] [|t = 8min] [|t = 18min] [|t = 29min] [|t = 43min] [|t = 1h 3min] [|t = 2h 32min] [|t = 23h 53min] [|t = 48h 10min] =Discussion= 1. Imine formation was fast (Complete within 5 min). Some imine reversal (**//how much//**) was observed upon the addition of acid and isocyanide. 2. After 2 days the reaction is about **//x% complete//**, based on the aldehyde peak at 9.5 ppm and isocyanide (CH2 t) at 4.68 ppm. 3. New peaks between 1.36-1.45 (2 doublets) ppm are consistent with the desired product, indicating that there are two NMR recognizable stereochemical configurations (out of 4 possible diasteromers) of the ugi product.
 * Exp115A**
 * Exp115B**

=Conclusion=

=Log=

2007-07-26
16:40 Measured out a solution of methylamine (250uL, 2.0M in CH3OH) in an NMR tube 16:45 Added 250uL of CD3OD to the NMR tube containing methylamine (50% CH3OH and 50%CD3OD) 16:47 Added furfural (41.5uL) to the NMR tube to obtain **115A** 16:52 Obtained HNMR of 115A (t = 5min) 16:54 Obtained HNMR of 115A (t = 7min) 21:43 Obtained HNMR of 115A (t = 4h 56min)

2007-07-27
17:26 Obtained HNMR of 115A (t = 24h 39min) 17:39 Added α,4-dimethylphenylacetic acid (82.1mg) and benzylisocyanide (60.6uL) in the NMR tube containing 115A, to obtain **115B** 17:47 Obtained HNMR of 115B (t = 8min) 17:57 Obtained HNMR of 115B (t = 18min) 18:08 Obtained HNMR of 115B (t = 29min) 18:22 Obtained HNMR of 115B (t= 43min) 18:42 Obtained HNMR of 115B (t = 1h 3min) 20:11 Obtained HNMR of 115B (t = 2h 32min)

2007-07-28
17:32 Obtained HNMR of 115B (t = 23h 53min); the solution in the NMR tube has turned deep brown in color..it does not appear that there is any solid in the tube

2007-07-28
17:57 Obtained HNMR of 115B (t = 48h 10min).. A small amount of a dark (brown/green) precipitate had settled down at the bottom of the tube, which dissolved back upon vigorous shaking.