Exp104

=Objective= To synthesize a [|Ugi adduct] from [|3,4-dimethoxybenzaldehyde], [|Furfurylamine], tertbutylisocyanide and [|Boc-Gly-OH] in methanol using Ugi 4CR. This reaction is a reaction redone Exp096 =Procedure= A solution of [|3,4-dimethoxybenzaldehyde] (veratradlehyde) (332 mg, 2 mmol) and f[|urfurylamine](FFA) (234.8 uL, 2.2 mmol, 10% excess ) was prepared in methanol-d4 in a 2mL volumetric flask to form an imine. After two hours a solution of [|Boc-Gly-OH](350 mg, 2 mmol), and [|tert-butyl isocyanide](226 uL, 2 mmol) madeup in a volumetric flask in methanol-d4 was added to the preformed imine. The product was filtered and washed with ice cold methanol (5mL) - The mother liquor was saved until it formed crystals again. C26H37N3O7; White solid; 1H NMR ( ppm, CDCl3) 1.34 (s, 9H), 1.45 (s, 9H), 3.76 (s, 3H), 3.87 (s, 3H), 4.22 (s, 2H), 4.48 (s, 2H), 5.49-6.12 (m, 5H) 6.71-6.88 (m, 3H), 7.20 (s, 1H) 13C NMR ( ppm, CDCl3) 28.3, 28.5, 42.0, 42.8, 51.6, 55.7, 55.8, 62.5, 79.5, 107.4, 110.4, 110.7, 112.6, 122.0, 126.7, 141.7, 148.9, 149.9, 150.0, 155.6, 168.7, 170.2; HRMS (FAB,//m-//nitrobenzyl alcohol): //m/z// calcd for C26H37N3O7 503.26, found 504.2725.

=Results= (Reactant NMRs from Exp054) [|H NMR] [|C NMR] [|H NMR] [|C NMR] [|H NMR] [|C NMR] [|H NMR] [|C NMR]
 * Veratradehyde**
 * Furfurylamine**
 * //tert-B//utyl isocyanide**
 * Boc-Gly-OH**

[|t = 17min] [|t = 24min] [|t = 32min] [|t = 34mim] [|t = 35min] [|t = 37min] [|t = 44min] [|t = 46min] [|t = 49min] [|t = 54min] [|t = 01h 00min] [|t = 01h 03min] [|t = 01h11min] [|t = 01h 16min] [|t = 01h 20min] [|t = 01h 23min] [|t = 01h 46min] CNMR [|DEPT] [|t = 01h 53min] CHs only [|t = 02h 01min] [|t = 02h 08min] [|t = 02min] [|t = 03min] [|t = 05min] [|t = 07min] [|t = 15min] [|t = 20min] [|t = 23min] [|t = 48min] [|t = 51min] [|t = 01h 00min] [|t = 02h 03min] [|H NMR] [|C NMR] [|C NMR (Image)] [|DEPT] [|All CH's] FAB MS [|Low Res] [|High Res]
 * 104A**
 * 104B**
 * 104C** (Batch-1 : 86.3mg, batch-2: 33.8mg) - **//you can't assume that 104C-2 is the same as 104C - need at least a separate HMR//**

=Discussion= Ugi products obtained from veratraldehyde tend to be more powdery than crystalline and are relatively more soluble in methanol than there benzaldehyde counterparts. =Conclusion= A ugi product was successfully synthesized in 12% yield. =Log=

2007-05-23
23:25 Madeup a solution of veratraldehyde and furfurylamine in 2 ml methanol-d4 in a volumetric flask to obtain **104A** 23:42 Obtained H NMR of 104A (t = 17min) 23:49 Obtained H NMR of 104A (t = 24min) 23:52 Obtained H NMR of 104A (t = 27min) 23:57 Obtained H NMR of 104A (t = 32min) 23:59 Obtained H NMR of 104A (t = 34min)

2007-05-24
00:00 Obtained H NMR of 104A (t = 35min) 00:02 Obtained H NMR of 104A (t = 37min) 00:09 Obtained H NMR of 104A (t = 44min) 00:11 Obtained H NMR of 104A (t = 46min) 00:14 Obtained H NMR of 104A (t = 49min) 00:19 Obtained H NMR of 104A (t = 54min) 00:25 Obtained H NMR of 104A (t = 01h 00min) 00:28 Obtained H NMR of 104A (t = 01h 03min) 00:36 Obtained H NMR of 104A ( t= 01h 11min) 00:41 Obtained H NMR of 104A (t = 01h 16min) 00:45 Obtained H NMR of 104A (t = 01h 20min) 00:48 Obtained H NMR of 104A (t = 01h 23min) 01:00 Made up a solution of Boc-Glycine and //tert-//Butylisocyanide in a 2 mL volumetric flask in 2 mL methanol-d4. 01:11 Obtained C NMR of 104A (t = 01h 46min) 01:18 Obtained DEPT of 104A (t = 01h 53min) 01:26 Obtained H NMR of 104A (t = 02h 01min) 01:33 Obtained H NMR of 104A (t = 02h 08min) 01:37 Added the previously made solution of Boc Glycine and tert-butyl isocyanide in methanol-d4 to 104A in a centrifuge tube, to obtain **104B**, 800uL of 104B was transferred back into the tube and the changes were monitored. 01:39 Obtained H NMR of 104B (t = 02min) 01:40 Obtained H NMR of 104B (t = 03min) 01:42 Obtained H NMR of 104B (t = 05min) 01:44 Obtained H NMR of 104B (t = 07min) 01:52 Obtained H NMR of 104B (t = 15min) 01:57 Obtained H NMR of 104B (t = 20min) 02:00 Obtained H NMR of 104B (t = 23min) 02:25 Obtained H NMR of 104B (t = 48min) 02:28 Obtained H NMR of 104B (t = 51min) 02:37 Obtained H NMR of 104B (t = 01h 00min) 03:40 Obtained H NMR of 104B (t = 02h 03min) 04:20 Solid had started to appear in the solution in the centrifiuge tube, at this time the solution from the NMR tube was poured into the centrifuge tube and set on a sonicator for 30min. 05:30 Almost the entire the solution in the centrifuge tube had solidified / looked like a white cake. 06:00 Removed the solid from the centrifuge tube into a beaker and rinsed out the centrifuge tube with methanol (2ml). The product in the beaker was set on a sonicator again and the enitre solid dissolved into it within a couple of minutes. 06:30 The beaker was parafilmed and left in the hood for crystallization. 13:00 Solid had appeared in the beaker with no traces of any methaol. 13:30 The solid in the beaker was removed from the beaker by using ice cold methanol (5ml) and the solvent was removed by filtering through a sintered glass funnel. 15:00 Obtained the solid **104C** (86.3mg) after air drying, the mother liquor **104D** was saved for further crystallization. 20:10 Obtained H NMR of 104C by dissolving 25 mg in 800uL of CDCl3.

2007-05-25
09:28 Obtained a C NMR of 104C from an overnight run. 16:20 After filteration of 104D, **104C-2** (33.8mg) of solid was obtained. Yield - 12% The filtered mother liquor is **104E**

2007-05-28
15:42 Obtained DEPT of 104C

=Tags= [|3,4-dimethoxybenzaldehyde] [|InChI=1/C9H10O3/c1-11-8-4-3-7(6-10)5-9(8)12-2/h3-6H,1-2H3] [|Furfurylamine] [|InChI=1/C5H7NO/c6-4-5-2-1-3-7-5/h1-3H,4,6H2] [|tert-butyl isocyanide][|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)] [|Product] [|InChI=1/C26H37N3O7/c1-25(2,3)28-23(31)22(17-11-12-19(33-7)20(14-17)34-8)29(16-18-10-9-13-35-18)21(30)15-27-24(32)36-26(4,5)6/h9-14,22H,15-16H2,1-8H3,(H,27,32)(H,28,31)]

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