Exp093



. =Objective= To synthesize a Ugi adduct from Benzophenone, Aniline, [|tert-butyl isocyanide] and [|Boc-Gly-OH] in methanol using Ugi 4CR. =Procedure= Dissolved benzophenone (182 mg, 1 mmol) and aniline(104.6 uL, 1.1 mmol, 10% excess ) in 2 mL methanol-d4 in a 4 mL volumetric flask, immediately transferred the contents to an NMR tube. The reaction was monitored by NMR. The reaction was left overnight to complete forming an imine. The next day a solution of [|Boc-Gly-OH]175 mg,1 mmol), and [|tert-butylisocyanide] (113 uL, 1 mmol) is made up in 4 ml volutmeric flask in methanol. This solution of is added to the preformed Imine. The reaction mix is allowed to sit undisturbed for 6-8, when the Ugi product is obtained. The product is recrystallized from a small amount of methanol analyzed by NMR and saved in a 1 dram vial. =Results= [|H NMR] [|C NMR](methanol-d4) spectrum does not appear decoupled - peaks showing up as doublets [|H NMR] [|C NMR] [|H NMR] [|C NMR] [|H NMR] [|C NMR] [|t = 04 min] [|t = 07 min] [|t = 09 min] [|t = 34 min] [|t = 41 min] [|t = 45 min] t[| = 55 min IR] [|t = 02 h 40 min] [|t = 02 h 45 min] [|t = 03 h 23 min] [|t = 03 h 44 min] [|t = 18 h 11 min] [|t = 18 h 32 min] [|H NMR] **(after 5days of addition of 92A to Boc-Gly and //tert-//butyl isocyanide)**
 * Aniline**
 * Benzophenone**
 * //tert-B//utyl isocyanide**
 * Boc-Gly-OH**
 * 93A**
 * 93B**

=Discussion= =Conclusion= Experiment aborted, (Imine did not form) =Log=
 * 1) There is no change in the H NMR even 18 h after mixing benzophenone with aniline and thus no evidence of imine formation. //**Compare this with other reports of imine formation - see refs page for reaction of aniline with ketones.**// The experiment has reached a dead end.
 * 2) Although before starting this reaction it was not known that aniline does not react with benzophenone under the conditions applied, however a reference[**1**] & [**2**] which indicates the unreactive behavior was found later.

2007-04-17
17:56 Made up a solution of solution of benzophenone and aniline in methanol-d4.**93A** 18:00 Obtained H NMR of 93A t = 04 min 18:03 Obtained H NMR of 93A t= 07 min 18:05 Obtained H NMR of 93A t= 09 min 18:30 Obtained C NMR of 93A t = 34 min 18:37 Obtained H NMR of 93A t = 41 min 18:41 Obtained H NMR of 93A t = 45 min 18:51 Obtained an IR of 93A t = 55 min 20:36 Obtained C NMR of 93A t = 02 h 40 min 20:41 Obtained HNMR of 93A t = 02 h 45 min 21:19 Obtained C NMR of 93A t = 03 h 23 min 21:40 Obtained H NMR of 93A t = 03 h 44 min

2007-04-18
12:07 Obtained H NMR of 93A t = 18 h 11 min 12:28 Obtained C NMR of 93A t = 18 h 32 min 12:40 Made up a solution of Boc Glycine and tert-butylisocyanide in a 2 ml volutmeric flask in methanol (**CH3OH**). 12:43 Added the aminoacid / isonitrile solution to 93A. This multicomponent reaction mixture is now labelled **93B**

2007-04-23
15:19 Obtained H NMR of 93B

=Ref= 1.Arndtsen, B., A.; Sleiman, H., F.; Chang, A., K.; McElwee-White, L.;J. Am. Chem. Soc., 1991, 113 (13), pp 4871–4876 **DOI:**[| 10.1021/ja00013a024] 2 Ross, N., A.; MacGregor, R., R.; Bartsch, R., A.; Tetrahedron, 60 (9) 23, pp 2035-2041; **DOI:** [|10.1016/j.tet.2004.01.002]

=Tags= [|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)]

media type="custom" key="93493"