Researchers

Hai Truong and Khalid Mirza

Objective

To measure the solubility of the Ugi product UC176C in methanol with a) phenanthrene-9-carbaldehyde b) furfurylamine and c) phenylacetic acid as co-solutes at different concentrations.

Procedure

  1. To ~1mL methanol in to a half dram vial add the Ugi product 176C; vortex the solution, make sure some of the solute remains undissolved. Place the solution in water/glycol bath at
0C, after 30min change the temp to 25C. Leave the sample in the bath for another 30min to equilibrate. Then centrifuge the sample vial and obtain the supernatant in DMSO-d6. Obtain HNMR of the solution
  1. Make-up a 0.053M solution of phenanthrene-9-carboxaldehyde in methanol, by dissolving 0.053mmol, 11mg in a 1mL volumetric flask.
  2. Make-up a 0.106M solution of phenanthrene-9-carboxaldehyde in methanol by dissolving 0.106mmol, 22mg in 1mL in a 1mL volumetric flask.
  3. Make-up a 0.113M solution of fufurylamine in methanol by dissolving 10uL furfurylamine (1.13mmol) in a 1mL volumetric flask.
  4. Make-up a 0.509M solution of furfurylamine in methanol by dissolving 45uL (5.11mmol) in a 1mL volumetric flask.
  5. Make-up a 0.870M solution of phenylacetic in methanol by dissolving 474mg (4mmol) in methanol in a 4mL volumetric flask (This is solution 150A)
  6. Dilute solution 150A to obtain 0.0435M, 0.0870M, 0.174M, 0.261M and 0.435M solutions (all ~ 1mL)
Calculations-link

Results

Spreadsheet-link

Discussion


Table -ONSExp150-i

NMR solution
number

Solution
source

co-solute
co-solute
conc (M)

SAMS conc
co-solute (M)

Ugi Product
Solubility (M)

ONSCExp150-1B
Exp150-1
None
--
--
0.01
ONSCExp150-2B
Exp150-2
None
--
--
0.01
ONSCExp150-3B
Flask 01
phenanthrene-9-
carboxaldehyde
0.053
0.03
0.01
ONSCExp150-4B
Flask 03
furfurylamine
0.113
0.12
0.01
ONSCExp150-5B
Flask 04
furfurylamine
0.509
0.43
0.01
ONSCExp150-6B
Flask 05
phenylacetic acid
0.431
0.05
0.01
ONSCExp150-7B
Flask 06
phenylacetic acid
0.087
0.09
0.01
ONSCExp150-8B
Flask 07
phenylacetic acid
0.174
0.19
0.01
ONSCExp150-9B
Flask 08
phenylacetic acid
0.261
0.26
0.01
ONSCExp150-10B
Flask 09
phenylacetic acid
0.435
0.44
0.01
There is no effect on the solubility the Ugi product UC176C when other co-solutes are present in its solution in methanol.
[Compare the pure Ugi product solution values with previous values in methanol - does it make sense? These new values also need to be added to the solsum sheet JCB]

Conclusion

Solubility of the Ugi product 176C remains unaffected by the type and concentration of co-solutes in methanol up to 0.43M furfurylamine, 0.44M phenylacetic acid or 0.03M phenanthrene-9-carboxaldehyde separately.

Log


2009-11-19
16:05 Took out 2 half dram vials, labeled Exp-150-1, Exp 150-2 and put into each approximately 1000ul methanol. Put small amount of Ugi product 176C into both vial so that there is still small mount of solid Ugi remain in the liquid.- Blanks
16:10 Parafilm both of them
16:20 Put them into Lauda heating/cooling bath. The current temperature in the bath was 30C. Adjust it to 40C.
16:40 Temperature in the bath was 40C
17:10 Adjusted temperature in the bath to 25C
17:25 Temperature reached 25C. Let them in the bath for whole night.

2009-11-20
12:05 Took out nine 1ml-volumetric-flasks and one 4ml volumetric flasks, cleaned with acetone and put into the oven for 5 minutes.
12:13 Took all the flasks out from the oven. Labeled from 1-9 for 1ml volumetric flasks, then:
For flask 01: Made-up a 0.053M solution of phenanthrene-9-carboxaldehyde in methanol, by dissolving 0.053mmol, 11mg in a 1mL volumetric flask.
For flask 02:Tried to make-up a 0.106M solution of phenanthrene-9-carboxaldehyde in methanol by dissolving 0.106mmol, 22mg in 1mL in a 1mL volumetric flask.- The solute did not dissolve in the solvent. Therefore, 0.1M solution of phenanthrene-9-carboxaldehyde in flask 2 is discarded.
For flask 03: Made-up a 0.113M solution of fufurylamine in methanol by dissolving 10uL furfurylamine (1.13mmol) in a 1mL volumetric flask.
For flask 04: Made-up a 0.509M solution of furfurylamine in methanol by dissolving 45uL (5.11mmol) in a 1mL volumetric flask.
In a 4ml volumetric flasks: Made-up a 0.870M solution of phenylacetic in methanol by dissolving 474mg (4mmol). This is solution- 150A.
For flask 05: From 150A solution, took 50ul transferred in to a 1mL volumetric flask, 05 and diluted it to 1ml by adding methanol. This is a 0.0431M phenylacetic acid solution.
For flask 06: From 150A solution, took 100ul transferred in to a 1mL volumetric flask, 06 and diluted to 1ml by adding methanol. This is a 0.0870M phenylacetic acid solution.
For flask 07: From 150A solution, took 200ul transferred in to a 1mL volumetric flask, 07 and diluted to 1ml by adding methanol. This is a 0.174M phenylacetic acid solution.
For flask 08: From 150A solution, took 300ul, transferred in to a 1mL volumetric flask, 08 and diluted to 1ml by adding methanol. This is a 0.261M phenylacetic acid solution.
For flask 09: From 150A solution, took 500ul transferred in to a 1mL volumetric flask, 09 and diluted to 1ml by adding methanol. This is a 0.435M phenylacetic acid solution.
14:20 Took out 8 half dram vials and labeled: Exp-150-3, Exp-150-4, Exp-150-5, Exp-150-6, Exp-150-7, Exp-150-8,Exp-150-9, Exp-150-10, in which:
Exp-150-3: Transferred from flask 01: 500ul of 0.053M solution of phenanthrene-9-carboxaldehyde in methanol and small amount of solute 176C
Exp-150-4: Transferred from flask 03: 500ul of 0.113M solution of fufurylamine in methanol in methanol and small amount of solute 176C
Exp-150-5: Transferred from flask 04: 500ul of 0.509M solution of furfurylamine in methanol and small amount of solute 176C
Exp-150-6: Transferred from flask 05: 500ul of 0.0431M solution of phenylacetic in methanol and small amount of solute 176C
Exp-150-7: Transferred from flask 06: 500ul of 0.0870M solution of phenylacetic in methanol and small amount of solute 176C
Exp-150-8: Transferred from flask 07: 500ul of 0.174M solution of phenylacetic in methanol and small amount of solute 176C
Exp-150-9: Transferred from flask 08: 500ul of 0.261M solution of phenylacetic in methanol and small amount of solute 176C
Exp-150-10: Transferred from flask 09: 500ul of 0.435M solution of phenylacetic in methanol and small amount of solute 176C
Note: There was still small amount of solute undissolved in each vial.
15:16 Parafilmed all of the vials.
15:30 Put all vials into Lauda heating/cooling bath. Adjusted temperature to 40C. There were totally 10 vials in the bath: 2 from last night and 8 from today.
16:00 Temperature in the bath was 40C. Lowered temperature to 25C.
16:25 Temperature reached 25C.
2009-11-21
13:10 Removed the vials from the temperature control bath.
13:35 Centrifuged the vials.
13:45 Carefully pipetted-out approximately 400uL of the supernatant from each vial and transferred then in to one dram vial containing 300uL DMSO-d6. The one dram vials were labeled ONSCExp150-1B, ONSCExp150-2B, ONSCExp150-3B, ONSCExp150-4B, ONSCExp150-5B, ONSCExp150-6B, ONSCExp150-7B, ONSCExp150-8B, ONSCExp150-9B and ONSCExp150-10B
16:50 Completed obtaining HNMRs for each of the ONSCExp150-#B solutions.


NMR solution number
Solution source
Cosolute Name
Cosolute conc(M)
SAMS conc of cosolute (M)
ONSCExp150-1B
Exp150-1
None
--
--
ONSCExp150-2B
Exp150-2
None
--
--
ONSCExp150-3B
Flask 01
phenanthrene-9-carboxaldehyde
0.053
0.03
ONSCExp150-4B
Flask 03
furfurylamine
0.113
0.12
ONSCExp150-5B
Flask 04
furfurylamine
0.509
0.43
ONSCExp150-6B
Flask 05
phenylacetic acid
0.431
0.05
ONSCExp150-7B
Flask 06
phenylacetic acid
0.087
0.09
ONSCExp150-8B
Flask 07
phenylacetic acid
0.174
0.19
ONSCExp150-9B
Flask 08
phenylacetic acid
0.261
0.26
ONSCExp150-10B
Flask 09
phenylacetic acid
0.435
0.44