Exp216

216-1 || =media type="custom" key="3547944"= 216-2 || =media type="custom" key="3547940"= 216-3 || = = media type="custom" key="3839615" 216-4 || 216-5 || =media type="custom" key="3547960"= 216-6 || =media type="custom" key="3547964"= 216-7 || = = media type="custom" key="3556650" 216-8 || 216-9 || = = media type="custom" key="3556654" 216-10 || media type="custom" key="3556658" 216-11 || media type="custom" key="3547980" 216-12 || 216-13 ||  ||   ||   ||
 * media type="custom" key="3547938"
 * =media type="custom" key="3547956"=
 * =media type="custom" key="3547968"=
 * media type="custom" key="3547988"

= = =Objective= To synthesize thirteen made Ugi products in methanol. The isolated products will be used to determine their solubility in different solvents.Three of these products have not been made previously.

=Procedure= To thirteen 4-dram vials, methanol was pipetted-out based on volume calculation for each component to be subsequently added, inorder to make a 0.5M solution per component for a 4C-Ugi reaction. For solid solutes calculated densities was obtained from Chemspider. An aldehyde and an amine were then reacted overnight in the vials. Then a carboxylic acid and an isocyanide was added to the vials. After the addition of each component, the vial was vortexed for at least 30s. All four components were added in equimolar ratio. The reaction mixtures were left overnight undisturbed. The solid precipitated out was then washed (3x0.3mL) and recrystallized from methanol. Structures were confirmed by NMR and melting points.


 * 216-10A:** N-[2-(cyclohexylamino)-1-(4-di​methylaminophenyl)-2-oxo-ethyl​]-N,3-dimethyl-benzamide: C25H33N3O2 ; White solid; 1H NMR ( ppm, 500MHz, CDCl3) 0.9-1.2 (m, 3H), 1.3-1.45 (m, 2H), 1.5-1.75 (m, 3H), 1.85-2.0 (m, 2H), 2.35 (s, 3H), 2.79 (s, 3H), 2.97 (s, 6H) 3.8-3.9 (m, 1H), 5.2-5.4 (m, 1H), 5.88 (bs, 1H), 6.25 (s, 1H), 6.6-6.8 (m, 2H), 7.1-7.4 (m, 5H); 13C NMR ([[image:http://pubs.acs.org/images/gifchars/delta.gif]] ppm, CDCl3) 21.2, 24.6,25.3, 32.8, 34.6, 40.2, 48.3, 60.1, 112.1, 122.0, 123.8, 127.5, 127.9, 130.0, 130.4, 136.3, 137.9, 150.1, 168.8, 172.1;HRMS (FAB): //m/z// calcd for C25H33N3O2 2Na (M+Na) 430.247047 Da, found 430.245077 Da; yield 18%

=Results= Spreadsheet [|UCExp216]

[|UCExp216-1A] [|UCExp216-2A] [|UCExp216-3A] [|UCExp216-4A] [|UCExp216-5A] [|UCExp216-7A] [|UCExp216-9A] [|UCExp216-6A] [|UCExp216-13A] UCExp216-12A
 * NMR**s

[|UCExp216-10A-HNMR]-500MHz [|UCExp216-10A-HNMR]-300MHz [|UCExp216-10A-CNMR] [|UCExp216-10A-Allprotonated Carbons] [|UCExp216-10A-DEPT] -JPG [|Nominal Mass FAB-MS] [|High Resolution FAB-MS]

media type="custom" key="3556156" =Discussion=

=Conclusion=

=Log=

2009-03-26
21:00 To 13 four dram vials, calculated amount of methanol was added..(listed in the spreadsheet above). Vials were labeled 216-1 to 216-12 and 216-14. 21:20 Calculated amount of the aldehyde was added to each vial, vortexed for 30s inorder to dissolve it, however phenanthrene-9-carboxaldehyde did not go in to the solution. Remaining solutions were clear. 22:25 Calculated amount of amine was added to each vial, vortexed for another 30s. Vials containing phenanthrene-9-carboxaldehyde were vortexed for 3min each..still some solid left undissolved in those vials...Remaining solutions were clear. 22:35 Parafilmed all the vials and left them to form imine over night.

2009-03-27
11:30 Calculated amount of carboxylic acid was added to each vial, vortexed for another 30s. Vials containing phenanthrene-9-carboxaldehyde were sonicated for 15min....all solutions were now clear..=> Acids were not added to solutions 216-8 and 216-10 (later) 13:00 Completed adding calculated amounts of the isocyanide to each vial...vortexed for 30s each..parafilmed the vials and left them in the hood. 13:05 Vials named 216-5 and 216-9 formed solid within 10mins. 13:09 Obtained a [|picture of the solutions] -- and [|another] 15:00 Vials 216-1 to 216-5 and 216-7 and 216-9 have already formed solid in them. 17:30 Carboxylic acid was added to vials 216-8 and 216-10, vortexed for 30s (clear soln obtained) then added isocyanide to each vials, vortexed for another 30s. 18:05 Obtained a picture of vials [|216-8 and 216-10]. 18:12 Obtained more pictures of all the solutions- [|Picture-1], [|Picture-2].

2009-03-29
18:00 Filtered out the solid from samples 216-1 to 216-5, 216-7 and 216-9, the residues were washed with 10mL methanol. Obtained The filtrate collected after methanol wash was accumulated as mother liquor for each sample. The mother liquors were called **216-#B**
 * 216-1A -**0.1646 g
 * 216-2A -**0.3539 g
 * 216-3A -**1.0038 g
 * 216.4A -**0.9322 g
 * 216-5A -**1.1437 g
 * 216-7A -**0.2371 g
 * 216-9A** -0.3580 g

2009-04-19
14:00 Vials 216-6, 216-10, 216-12, and 216-13 had developed solid, the liquid in these vials was decanted into a new vials and the solid was washed with methanol (3x 1mL). Each time after vortexing for 30s the supernatant was decanted and the solid was washed further. The solid obtained after washing was left in the desiccator to dry. 15:00 Removed the solids from the desiccator and weighed them. The solids are now named 216-6A, 216-10A, 216-3A. Obtained
 * 216-6A** - 0.227g
 * 216-13A** - 0.275g
 * 216-10A** -0.291g