exp063

== =Objective= To synthesize a Ugi adduct(**//link//**) with [|3,4-dihydroxybenzaldehyde], [|5-methylfurfurylamine], [|tert-butylisocyanide] and [|Boc-Gly-OH] in deuterated methanol.

=Procedure= Dissolved 3,4-dihydroxybenzaldehyde (2 mmol, 276 mg) and 5-methylfurfurylamine (2.2 mmol, 245 uL) in 4 mL CD3OD in a 4 mL volumetric flask, immediately transferred the contents to a 25mL Erlenmeyer flask, and removed 800 uL to obtain initial HMR spectra. The material used to obtain the H NMRs was returned to the Erlenmeyer, and the reaction was allowed to sit overnight without stirring to preform the imine. Boc-Gly-OH (2 mmol, 350 mg) was added to the mixture, and the reaction was swirled for approximately 30 seconds in order to dissolve the reagent. After approximately 15 minutes, t-butyl isocyanide (2 mmol, 226 uL) was added to the mixture and swirled for approximately 30 seconds. The progression of the reaction was monitored by H NMR.

=Results= (*Spectra obtained on a Varian Inova 300 MHz instrument, unless specified otherwise) [|H NMR] (CD3OD, from exp047) [|H NMR] (CD3OD, from exp047) [|H NMR] (CD3OD, from exp054) [|H NMR] (CD3OD, from exp052)
 * 3,4-Dihydroxybenzaldehyde**
 * 5-Methylfurfuylamine**
 * Boc-Gly-OH**
 * tert-Butylisocyanide**

[|H NMR] (t=2 min) [|H NMR] (t=18 min) [|H NMR] (t=42 min) [|H NMR] (t=20 h 12 min) [|H NMR] (t=15 min) [|H NMR] (t=26 min) [|H NMR] (t=33 min) [|H NMR] (t=46 min) [|H NMR] (t=1 h) [|H NMR] (t=3 h, 41 min) [|H NMR] (t=25 h 44 min) (Varian 500 MHz H NMR, TMS peak referenced wrong because it was too faint)
 * 63A (after aldehyde and amine)**
 * 63B (after boc-gly)**
 * 63C (after isonitrile)**

Spectral Overlays
[|Addition of isocyanide]

Reaction Profiles
=Discussion= =Conclusion= = = = = =Log=
 * 1) note effect of adding boc-gly on imine/aldehyde/amine ratios and link to other experiments that did or did not demonstrate similar behavior
 * 2) does it look like the Ugi product forms?

2007-02-28
18:45 Dissolved 3,4-dihydroxybenzaldehyde in a minimal volume of CD3OD in a 4 mL volumetric flask. Added 5-methylfurfurylamine, diluted to 4 mL, transferred to a 25 mL Erlenmeyer flask, swirled for 15 seconds, and immediately removed 800 uL for H NMR spectra (**63A**). 18:59 Obtained H NMR spectra of imine mixture **63A** (t=2 min). 19:15 Obtained H NMR spectra of imine mixture **63A** (t=18 min). 19:38 Obtained H NMR spectra of imine mixture **63A** (t=42 min).

2007-03-01
15:08 Obtained spectra of imine mixture **63A** (t=20h 12 min). 15:55 Added Boc-Gly-OH (**63B**). 16:10 Obtained H NMR spectra of mixture **63B** (t=15 min). 16:20 Added t-butylisocyanide (**63C**). 16:46 Obtained H NMR spectra of mixture **63C** (t=26 min). 16:53 Obtained H NMR spectra of mixture **63C** (t=33 min). 17:06 Obtained H NMR spectra of mixture **63C** (t=46 min). 17:20 Obtained H NMR spectra of mixture **63C** (t=1h). 20:41 Obtained H NMR spectra of mixture **63C** (t=3h 41 min).

2007-03-02
18:44 Obtained H NMR spectra of mixture **63C** (t=25 h 44 min, on 500 MHz machine).

2007-03-03
17:07 A small amount of solid had formed in the flask. 17:30 Added 250 uL hexanes and 250 uL chloroform to the solution and put on ice in to attempt to draw more solid from the solution. 18:00 Suction filtered through a Buechner funnel, rinsed with a minimal amount of cold methanol, to yield white crystals. Allowed filter paper and solid to dry with suction. 18:30 The weight of the crude crystals (on tared filter paper) was determined to be 30 mg.

2007-03-25
22:00 Dissolved 63C in 1 mL CD3OD (didn't seem to dissolve), transferred 800 uL to a clean NMR tube. 22:20 Unable to obtain a good NMR, could not recover product, will attempt again in another experiment (exp106).

=Tags= [|3,4-dihydroxybenzaldehyde] [|InChI=1/C7H6O3/c8-4-5-1-2-6(9)7(10)3-5/h1-4,9-10H] [|5-methylfurfurylamine] [|InChI=1/C6H9NO/c1-5-2-3-6(4-7)8-5/h2-3H,4,7H2,1H3] [|tert-butylisocyanide] [|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)]