Exp185scheme.jpg

Objective

To synthesize two Ugi adducts from in methanol using Ugi 4CR following Explan005. If solid products are obtained, the experiment will serve as a template for an automated run.

Procedure

To two one dram vials, charged with methanol (1mL), 4- (trifluoromethyl benzaldehyde (0.5mmol), respective amines (0.5mmol), methactrylic acid (0.5mmol) and t-butyl isocyanide (0.5mmol) was added in that order. After each addition, the resulting solution was vortexed for 15 seconds and confirmed that a homogeneous solution had been obtained. The vial was capped tight and left at room temperature.
Sample ID
Aldehyde
Amine
Acid
Isocyanide
Ppt (Y/N) & Yield
185-1
4- (trifluoromethyl) benzaldehyde
(0.5mmol-68.3uL)
5-Methylfurfurylamine
(0.5mmol-55.7uL)
Methacrylic acid
(0.5mmol-42.4uL)
t-butylisocyanide
(0.5mmol-56.5uL)
N
185-2
4- (trifluoromethyl) benzaldehyde
(0.5mmol-68.3uL)
Benzylamine
(0.5mmol-54.5uL)
Methacrylic acid
(0.5mmol-42.4uL)
t-butylisocyanide
(0.5mmol-56.5uL)
N

Results

Exp ID
Day1
Day-2
Final
185-1
185-day1.JPG
185-1day2.JPG
No ppt
185-2
185-day1.JPG
185-2day2.JPG
No ppt

Discussion

After 4 days of waiting both solutions remained clear with no crystallization..Since there are no reagent solubilities involved when using liquid reagents in methanol, it may be worth while to increase the concentrations of the reagents from 0.5mmol per reagent in 1ml methanol to 2mmol per reagent in 1ml methanol...Exp 187.
It may also be worth going more dilute to about 0.25 M since it has been observed that Ugi products that precipitate at this concentration do not at higher concentration....Exp188

Conclusion

For the reagents on hand and the concentration used a solid ugi product was not isolable.

Log

2008-05-05
15:00 Charged two vials labelled 185-1 and 185-2 with methanol (1ml) each. Added 4-(trifluoromethyl) benzaldehyde (0.5mmol, 68.3uL) to each vial, and vortexed for 15s. Then added 5-methyl furfurylamine (0.5mmol-42.4uL) to vial 185-1 and benzylamine (0.5mmol, 54.6uL) to vial 185-2. Both the vials were vortexed for 15 s each. A clear solution was obtained in both cases. Then to each vial methacrylic acid (0.5mmol, 42.4ul) followed by t-butyl isocyanide (0.5mmol, 56.5uL) was added. After each addition the solutions were vortexed for 15s.
15:43 Obtained a picture of the solutions.
2008-05-06
10:30 Vortexed the solutions for 30s each and obtained a picture of each. No ppt still.....
2008-05-08
19:00 After 4 days neither of the solutions have any precipitates..

Tags

Chemical
Inchi
Inchikey
4- (trifluoromethyl benzaldehyde
InChI=1/C8H5F3O/c9-8(10,11)7-3-1-6(5-12)2-4-7/h1-5H
BEOBZEOPTQQELP-UHFFFAOYAG
5-Methylfurfurylamine
InChI=1/C6H9NO/c1-5-2-3-6(4-7)8-5/h2-3H,4,7H2,1H3
YSEAGSCGERFGBL-UHFFFAOYAH
Benzylamine
InChI=1/C7H9N/c8-6-7-4-2-1-3-5-7/h1-5H,6,8H2
WGQKYBSKWIADBV-UHFFFAOYAL
Methacrylic acid
InChI=1/C4H6O2/c1-3(2)4(5)6/h1H2,2H3,(H,5,6)
CERQOIWHTDAKMF-UHFFFAOYAE
t-butyl isocyanide
InChI=1/C5H9N/c1-5(2,3)6-4/h1-3H3
FAGLEPBREOXSAC-UHFFFAOYAL
185-2
InChI=1/C24H27F3N2O2/c1-16(2)22(31)29(15-17-9-7-6-8-10-17)20(21(3 ​0)28-23(3,4)5)18-11-13-19(14-12-18)24(25,26)27/h6-14,20H,1,15H2,2​ -5H3,(H,28,30)
KPGSTEQWODPHDS-UHFFFAOYAL
185-1
InChI=1/C23H27F3N2O3/c1-14(2)21(30)28(13-18-12-7-15(3)31-18)19(20 ​(29)27-22(4,5)6)16-8-10-17(11-9-16)23(24,25)26/h7-12,19H,1,13H2,2​ -6H3,(H,27,29)
SAWKKHAHHFXDJA-UHFFFAOYAY