Experiment 264 - Synthesis of Ugi 233 and Ugi 234 Repeat

Researcher

David Bulger- dbulger dbulger
Reactants
Product

Ugi 233


Ugi 234

Objective

To synthesize Ugi 233 and Ugi 234 in a 1.0 M solution of methanol in order to calculate the yield and obtain more product for further analyses.

Procedure

Ugi 233 was synthesized by combining 4.58 mmol of benzylamine (ChemSpider), 3,5-dimethoxybenzaldehyde(Chemspider), phenylpropiolic acid(ChemSpider), and cyclohexylisocyanide(ChemSpider) in 2.29 mL of methanol. And Ugi 234 was synthesized by combining 4.58 mmol of benzylamine (ChemSpider), 3,5-Bis(trifluoromethyl)benzaldehyde(ChemSpider), phenylpropiolic acid(ChemSpider), and cyclohexylisocyanide(ChemSpider) in 2.22 mL of methanol. Products will be vortexed, centrifuged, and the supernatant will be decanted and analyzed by 1H NMR. Methanol will then be added incrementally until the NMR shows that the reactants have been removed. The NMR will also be used to determine how much product is being removed in each washing and what other impurities are present. After the product has been purified, the vials will be dessicated and the pure yield will be calculated using the final weight of the reaction vials, the supernatant NMRs, and the solubility of the products in methanol. Finally, the pure product will be analyzed by 1H NMR and IR to confirm the identities of the product. All reactants, except cyclohexylisocyanide, will also be analyzed by 1H NMR, 13C NMR, and IR to confirm the identity of reactant signals.

Results

Photos

Reaction_vials
post-reaction_vials_1 (Ugi 233 reaction vials 5 minutes after addition of last reagent)
post-reaction_Ugi_233_vial_2 (Ugi 233 reaction vial 3 hours later)
post-reaction_Ugi_234_vial_2 (Ugi 234 reaction vial 3 hours later)
Ugi_Wash_1
Ugi_Wash_1_with_empty_vials
Ugi_Wash_1_afterwards
Ugi_Wash_2_immediately_after
Ugi_Wash_2.1
Ugi_Wash_2.2
Ugi_Wash_2.4
Ugi_Wash_3.1
Ugi_Wash_3.2

Characterization

3,5-Dimethoxybenzaldehyde


IR between KCl discs


NMR




Phenylpropiolic acid

IR between KCl discs


NMR




3,5-Bis(trifluoromethyl)benzaldehyde

IR between KCl discs


NMR




Benzylamine

IR between KCl discs


NMR




Methanol



Note: Peaks seem too broad here. I will recollect the spectrum soon.
Ugi 233 Wash Solution #1


Ugi 233 Wash Solution #2


Ugi 233 Wash Solution #3


Ugi 234 Wash Solution #1


Ugi 234 Wash Solution #2


Ugi 234 Wash Solution #3


Note: Peaks seem too broad here. I will recollect the spectrum soon.
Yield

Discussion

Added a little too much cyclohexylisocyanide to the Ugi 233 reaction vial and therefore too little to the Ugi 234 reaction vial due to the limited supply of cyclohexylisocyanide (1-g). This decreased the predicted yield for Ugi 234 and prevented the reaction from being equimolar.

Conclusion

Log

2011-03-30

10:30 - Weighed empty reaction vials for Ugi 233 (29.8900 g) and Ugi 234 (28.8894 g)
10:37 - Photo of reaction vials (Reaction_vials)

Ugi 233
Ugi 234
Methanol (mL)
2.29
2.22
Benzylamine (mL)
0.50
0.50
Aldehyde
0.7612 g
0.76 mL
Carboxylic acid (g)
0.6695
0.6696
Cyclohexylisocyanide (mL)
0.59
0.55
12:24 - Added the last reagent (cyclohexylisocyanide)
12:29 - Photos of reaction vials (post-reaction_vials_1)
14:35 - Photos of reaction vials (post-reaction_Ugi_233_vial_2, post-reaction_Ugi_234_vial_2)

2011-04-06

15:50 - Cleaned outside of vials and placed in vacuum desiccator to remove any traces of cyclohexylisocyanide.

2011-04-07

12:00 - Removed vials from vacuum desiccator and cleaned desiccator to remove any residual cyclohexylisocyanide.
12:15 - Weighed Ugi 233 (34.0735 g) and Ugi 234 vials (33.5828 g).
12:23 - Weighed two 20-mL vials for Ugi 233 (14.6250 g) and Ugi 234 (14.0277 g).
12:30 - Transferred Ugi 233 in 5-mL vial to a 20-mL vial while washing the Ugi 233 5-mL vial with about 20-mL methanol (lost a very small amount of product in this step).
14:00 - Left vials (5-mL Ugi 234 vial and 20-mL Ugi 233 vial) in hood to allow some of the methanol in the Ugi 233 vial to evaporate (Photo).

2011-04-12

8:37 - Collected FT-IR for 3,5-dimethoxybenzaldehyde between KCl discs.
9:20 - Collected FT-IR for phenylpropiolic acid between KCl discs.
9:52 - Collected FT-IR for 3,5-bis(trifluoromethyl)benzaldehyde between KCl discs.
10:09 - Collected 1H FT-NMR for 3,5-bis(trifluoromethyl)benzaldehyde.
10:13 - Collected FT-IR for benzylamine between KCl discs.
10:59 - Collected 13C FT-NMR for 3,5-bis(trifluoromethyl)benzaldehyde.
11:30 - Transferred Ugi 235 in 5-mL vial to a 20-mL vial while washing the Ugi 234 5-mL vial with about 20-mL methanol (lost a very small amount of product in this step).
12:09 - Photo of 20-mL vials (Ugi_Wash_1).
13:54 - Collected 1H FT-NMR for benzylamine.
14:00 - Collected 13C FT-NMR for benzylamine.
14:27 - Photo of 20-mL vials with the corresponding empty vials for the supernatant from wash #1 (Ugi_Wash_1_with_empty_vials).
14:30 - Weighed the empty wash #1 vials for Ugi 233 (20.2764 g) and Ugi 234 (20.5171 g).
14:39 - Transferred supernatant in 20-mL vials to corresponding wash #1 vials (Ugi_Wash_1_afterwards).
14:42 - Weighed the wash #1 vials with the supernatant for Ugi 233 (30.0985 g) and Ugi 234 (29.0485 g)
14:43 - Weighed the post-wash #1 20-mL vials for Ugi 233 (23.5467 g) and Ugi 234 (22.8259 g)
14:53 - Collected 1H FT-NMR for 3,5-dimethoxybenzaldehyde.
15:02 - Collected 13C FT-NMR for 3,5-dimethoxybenzaldehyde.
15:13 - Added about 20-mL methanol to each 20-mL vial for Ugi 233 and Ugi 234 (Ugi_Wash_2_immediately_after)
15:15 - Weighed the 20-mL vials with wash #2 methanol for Ugi 233 (30.6955 g) and Ugi 234 (29.8384 g)
15:52 - Collected 1H FT-NMR for phenylpropiolic acid.
16:03 - Photos of 20-mL vials with wash #2 (Ugi_Wash_2.1; Ugi_Wash_2.2).
16:38 - Collected 13C FT-NMR for phenylpropiolic acid.
16:59 - Collected 1H FT-NMR for methanol used in the reaction and the washing.

2011-04-13

16:35 - Photo of vials after settling.
16:50 - Photo of empty wash #2 vials.
17:00 - Weighed vials for Ugi 233 Wash #1 (30.0973 g) and Ugi 234 Wash #1 (29.0472 g).
17:05 - Added 500 μL CDCl3 and 10 μL TMS to NMR tube (NMR233W1).
17:08 - Weighed NMR233W1 (3.5557 g).
17:09 - Added 500 μL of Ugi 233 Wash #1 solution to NMR233W1.
17:13 - Weighed NMR233W1 (3.9700 g).
17:16 - 1H FT-NMR for Ugi233Wash1.
17:20 - Added 500 μL CDCl3 and 10 μL TMS to NMR tube (NMR234W1).
17:25 - Weighed NMR234W1 (3.6258 g).
17:27 - Added 500 μL of Ugi 234 Wash #1 solution to NMR234W1.
17:33 - Weighed NMR234W1 (4.0709 g).
17:42 - 1H FT-NMR for Ugi234Wash1.
17:45 - Weighed vials for Ugi 233 (30.5700 g) and Ugi 234 (29.7706 g).
17:49 - Weighed vials for Ugi 233 Wash #2 (16.2819 g) and Ugi 234 Wash #2 (14.7160 g).
17:51 - Photo of vials after removing supernatant (Ugi_Wash_2.4).
17:55 - Weighed vials for Ugi 233 (24.4158 g) and Ugi 234 (21.8316 g).
17:56 - Weighed vials for Ugi 233 Wash #2 (22.2308 g) and Ugi 234 Wash #2 (22.4651 g).
18:00 - Added 500 μL CDCl3 and 10 μL TMS to NMR tube (NMR233W1).
18:05 - Weighed NMR233W2 (3.6499 g).
18:07 - Added 500 μL of Ugi 233 Wash #2 solution to NMR233W2.
18:21 - 1H FT-NMR for Ugi233Wash2.
17:05 - Added 500 μL CDCl3 and 10 μL TMS to NMR tube (NMR234W2).
17:08 - Weighed NMR234W2 (3.5381 g).
17:09 - Added 500 μL of Ugi 234 Wash #2 solution to NMR234W2.
17:13 - Weighed NMR234W2 (3.9353 g).
18:40 - 1H FT-NMR for Ugi234Wash2.
19:07 - Photo of vials with methanol added and mixed (wash #3) (Ugi_Wash_3.1).
19:09 - Weighed NMR233W2 (4.0621 g).
19:11 - Added about 20-mL methanol to Ugi 233 and Ugi 234 vials.
19:15 - Weighed vials for Ugi 233 (30.4497 g) and Ugi 234 (29.6948 g).
19:22 - Photo vials (wash #3) (Ugi_Wash_3.2).

2011-04-18

Video of lab work will be uploaded soon.
Weighed empty wash #3 vials for Ugi 233 (14.9844 g) and Ugi 234 (14.8726 g).
Transferred supernatant from product vials to wash #3 vials.
Weighed product vials for Ugi 233 (22.6260 g) and Ugi 234 (22.6851 g).
Weighed wash #3 vials for Ugi 233 (22.5299 g) and Ugi 234 (21.6591 g).
Added 500 μL CDCl3 and 10 μL TMS to NMR tube for Ugi 233 (NMR233W3) and Ugi 234 (NMR234W3).
Weighed NMR233W3 (3.4812 g) and NMR234W3 (3.5523 g).
Added 500μL of Ugi 233 to NMR233W3 and 500μL of Ugi 234 to NMR234W3.
Weighed NMR233W3 (3.9422 g) and NMR234W3 (3.9455 g).
1H FT-NMR for Ugi233Wash3.
1H FT-NMR for Ugi234Wash3.
Added methanol to product vials for Ugi 233 and Ugi 234.
Weighed product vials for Ugi 233 (30.5147 g) and Ugi 234 (30.3079 g).

2011-04-29

19:30 - Weighed empty wash#4 vials for Ugi 233 (14.6397 g) and Ugi 234 (14.6209 g).
Weighed empty wash#5 vials for Ugi 233 (14.5050 g) and Ugi 234 (14.3978 g).
Transferred supernatant from product vials to wash#4 vials for Ugi 233 and Ugi 234.
Weighed wash#4 vials after transfer for Ugi 233 (24.2029 g) and Ugi 234 (22.7353 g).
Weighed product vials for Ugi 233 (20.5288 g) and Ugi 234 (22.0394 g).
Added methanol to product vials for Ugi 233 and Ugi 234.
22:30 - Transferred supernatant from product vials to wash#5 vials for Ugi 233 and Ugi 234.
Weighed wash#5 vials after transfer for Ugi 233 (21.1486 g) and Ugi 234 (21.4831 g).
Weighed product vials for Ugi 233 (23.2024 g) and Ugi 234 (22.7588 g).
Transferred more supernatant from product vials to wash#5 vials for Ugi 233 and Ugi 234.
Weighed wash#5 vials after second transfer for Ugi 233 (26.5913 g) and Ugi 234 (23.4224 g).
Weighed product vials for Ugi 233 (17.4907 g) and Ugi 234 (20.5949 g).
Desiccated Ugi 233 and Ugi 234 vials in a heated vacuum desiccator until dry
(Note: For about 10 minutes both vials remained steady, then both solutions in Ugi 233 and Ugi 234 exploded out of the vials coating the inside of the desiccator with Ugi 233 and Ugi234.)
Weighed left-over dry product vials for Ugi 233 (15.3254 g) and Ugi 234 (15.2810 g).
Cleaned up the desiccator and other equipment used in this experiment.

References

Bulger, David. Synthesis and Characterization of Ugi 233. <http://usefulchem.wikispaces.com/Exp233>
Bulger, David. Synthesis and Characterization of Ugi 234. <http://usefulchem.wikispaces.com/Exp234>

Tags

Ugi 233
Tag
Google
SMILES:
coc1cc(cc(c1)oc)c(c(%3Do)nc2ccccc2)n(cc3ccccc3)c(%3Do)c%23cc4ccccc4
Google Search
InChI:
inchi=1/c32h34n2o4/c1-37-28-20-26(21-29(22-28)38-2)31(32(36)33-27-16-10-5-11-17-27)34(23-25-14-8-4-9-15-25)30(35)19-18-24-12-6-3-7-13-24/h3-4,6-9,12-15,20-22,27,31h,5,10-11,16-17,23h2,1-2h3,(h,33,36)
Google Search
InChIKey:
azlbtwfvmdzyln-uhfffaoyar
Google Search
Std. InCh:
inchi=1s/c32h34n2o4/c1-37-28-20-26(21-29(22-28)38-2)31(32(36)33-27-16-10-5-11-17-27)34(23-25-14-8-4-9-15-25)30(35)19-18-24-12-6-3-7-13-24/h3-4,6-9,12-15,20-22,27,31h,5,10-11,16-17,23h2,1-2h3,(h,33,36)
Google Search
InChIKey:
azlbtwfvmdzyln-uhfffaoysa-n
Google Search

Ugi 234
Tag
Google
SMILES:
c1ccc(cc1)cn(c(c2cc(cc(c2)c(f)(f)f)c(f)(f)f)c(%3Do)nc3ccccc3)c(%3Do)c%23cc4ccccc4
Google Search
InChI:
inchi=1/c32h28f6n2o2/c33-31(34,35)25-18-24(19-26(20-25)32(36,37)38)29(30(42)39-27-14-8-3-9-15-27)40(21-23-12-6-2-7-13-23)28(41)17-16-22-10-4-1-5-11-22/h1-2,4-7,10-13,18-20,27,29h,3,8-9,14-15,21h2,(h,39,42)
Google Search
InChIKey:
uyxaplvgiotmnk-uhfffaoyap
Google Search
Std. InCh:
inchi=1s/c32h28f6n2o2/c33-31(34,35)25-18-24(19-26(20-25)32(36,37)38)29(30(42)39-27-14-8-3-9-15-27)40(21-23-12-6-2-7-13-23)28(41)17-16-22-10-4-1-5-11-22/h1-2,4-7,10-13,18-20,27,29h,3,8-9,14-15,21h2,(h,39,42)
Google Search
InChIKey:
uyxaplvgiotmnk-uhfffaoysa-n
Google Search